CN102597181B - Processes for hydromethanation of a carbonaceous feedstock - Google Patents

Abstract

The present invention relates to processes for preparing gaseous products, and in particular a hydrogen product stream and optionally a methane product stream, via the hydromethanation of carbonaceous feedstocks in the presence of steam, carbon monoxide, hydrogen and a hydromethanation catalyst.

Description

The hydrogenation methanation method of carbon raw material

Invention field

The present invention relates to one under steam, carbon monoxide, hydrogen and hydrogenation methanation catalyst exist, by the hydrogenation methanation of carbon raw material, prepare gaseous product, the method that particularly hydrogen product stream and optional methane product flow.

Background of invention

Consider that many factors is such as higher energy prices and environmental concern, by produce increment gaseous product compared with the carbon raw material of low fuel value (such as petroleum coke, coal and biomass), just again receive publicity.These material catalytic gasifications are disclosed in to for example US3828474 to produce methane with other increment gas, US3958957, US3998607, US4057512, US4092125, US4094650, US4204843, US4243639, US4468231, US4500323, US4541841, US4551155, US4558027, US4606105, US4617027, US4609456, US5017282, US5055181, US6187465, US6790430, US6894183, US6955695, US2003/0167961A1, US2006/0265953A1, US2007/000177A1, US2007/083072A1, US2007/0277437A1, US2009/0048476A1, US2009/0090056A1, US2009/0090055A1, US2009/0165383A1, US2009/0166588A1, US2009/0165379A1, US2009/0170968A1, US2009/0165380A1, US2009/0165381A1, US2009/0165361A1, US2009/0165382A1, US2009/0169449A1, US2009/0169448A1, US2009/0165376A1, US2009/0165384A1 and GB1599932.Also referring to people such as Chiaramonte, " Upgrade Coke by Gasification (by the gasification coke of upgrading) ", Hydrocarbon Processing (hydrocarbon processing), September nineteen eighty-two, 255-257 page; With people such as Kalina, " Exxon Catalytic Coal Gasification Process Predevelopment Program; Final Report (plan before the exploitation of Exxon catalysis coal gasification method; final report) ", Exxon Research and Engineering Co., Baytown, TX, FE236924, in December, 1978.

Generally speaking, under the temperature and pressure raising, under catalyst source and steam existence, by the reaction of material, carbonaceous material (such as coal, biomass, asphaltene, liquid petroleum resistates and/or petroleum coke) can be converted into multiple gases, comprises that increment gas is such as methane.By cooling unstripped gas and wash in multiple processes, to remove by product (such as hydrogen and carbon monoxide) and less desirable pollutent (comprising carbonic acid gas and hydrogen sulfide), with production methane product, flow.

Carbon source is usually directed to four independent reactions to the hydrogenation methanation of methane:

Steam carbon: C+H ₂o → CO+H ₂(I)

Water-gas transforms: CO+H ₂o → H ₂+ CO ₂(II)

CO methanation: CO+3H ₂→ CH ₄+ H ₂o (III)

Hydrogasification: 2H ₂+ C → CH ₄(IV)

In hydrogenation methanation reaction, first three reaction (I-III) is taken as the leading factor and is shown lower total reaction:

2C+2H ₂O→CH ₄+CO ₂ (V)。

This total reaction is essentially thermally equilibrated; But, due to process calorific loss and other energy requirement (such as need to enter the moisture evaporation of reactor together with raw material), must add some heats to keep thermal equilibrium.

This reaction is also essentially (synthetic gas produces and consumes) of synthetic gas (hydrogen and carbon monoxide) balance; Therefore, because carbon monoxide takes out together with product gas with hydrogen, need to as required carbon monoxide and hydrogen be joined in reaction, to avoid shortage.

For the net heat that keeps reaction approaches neutral (only heat release or heat absorption a little) as far as possible, and keep synthetic gas balance, conventionally the overheated gas stream of steam, carbon monoxide and hydrogen is fed to hydrogenation methanator.Usually, carbon monoxide is the recirculation flow Fen Li from product gas with hydrogen stream, and/or by a part of product methane reforming is provided.Referring to for example US4094650, US6955595 and US2007/083072A1.

The reformation that separates recycle gas (for example passing through low-temperature distillation) and methane product from methane product improves raw methanogenic engineering complexity and resulting cost greatly, and reduces total system efficiency.

Steam generation is another region of improving the engineering complexity of total system.For example, use the boiler of external firing can greatly reduce total system efficiency.

Wherein eliminate or improve gas re-circulation loop and effectively produce steam and be described in the improved hydrogenation methanation method that reduces raw methanogenic complicacy and cost the US2009/0165376A1 being incorporated to above, US2010/0120926A1, US2010/0071262A1, US2010/0076235A1 and WO2010/048493A2, and own together and the U.S. Patent Application Serial Number 12/778 of pending trial simultaneously, 538 (the reel number FN-0047 US NP1 of agency, be entitled as PROCESSES FOR HYDROMETHANATION OF A CARBONACEOUS FEEDSTOCK (for the method for the hydrogenation methanation of carbon raw material)), 12/778, 548 (the reel number FN-0048 US NP1 of agency, be entitled as PROCESSES FOR HYDROMETHANATION OF A CARBONACEOUS FEEDSTOCK (for the method for the hydrogenation methanation of carbon raw material)) and 12/778, 552 (the reel number FN-0049 US NP1 of agency, be entitled as PROCESSES FOR HYDROMETHANATION OF A CARBONACEOUS FEEDSTOCK (for the method for the hydrogenation methanation of carbon raw material)), they separately on May 12nd, 2010 submit to.

In hydrogenation methanation reaction, as mentioned above, result is the raw produce gas stream of " directly " methane rich, and it can subsequent purificn further methane rich, so that final methane product to be provided.These are different from conventional gasification process, such as those of the partial combustion/oxidation based on carbon source, wherein synthetic gas (carbon monoxide+hydrogen) is main products (seldom or do not have methane direct production), it can further be processed subsequently, to produce methane (by catalytic production of methane, referring to reaction (III)) or any amount of other higher hydrocarbon product.

Because hydrogen is the synthesis gas components of conventional gasification process, these methods are also applicable to hydrogen gas production.

When methane is the finished product of expecting, hydrogenation methanation reaction provides the possibility of the efficiency that improves than traditional gasification process and lower methane cost.

Although hydrogen is the potential by product of aforementioned hydrogenation methanation method, such as the US2009/0259080A1 for example owning together and the U.S. Patent Application Serial Number 12/778 that is incorporated to above, 548 is disclosed, but can expect to produce hydrogen as primary product, and some (or not having) methane are as by product, keep the hydrogenation methanation method efficiency relative with traditional gasification process and other benefit simultaneously.The invention provides such hydrogen production process.

Summary of the invention

On the one hand, the invention provides by carbon raw material and produce multiple gaseous product and produce the method that hydrogen product flows, said method comprising the steps of:

(a) to hydrogenation methanator, supply

(1) carbon raw material,

(2) hydrogenation methanation catalyst,

(3) vapour stream,

(4) feed gas stream and

(5) the first optional oxygen enriched gas stream;

(b) under carbon monoxide, hydrogen, steam, hydrogenation methanation catalyst and optional oxygen exist, in hydrogenation methanator, make carbon raw material reaction, to produce the raw produce stream of the methane rich that comprises methane, carbon monoxide, hydrogen, carbonic acid gas, hydrogen sulfide and heat energy;

(c) from described hydrogenation methanator, take out the raw produce stream of described methane rich;

(d) the raw produce stream of described methane rich is introduced in First Heat Exchanger unit, with the raw produce stream from described methane rich, removed heat energy;

(e) acid transforms the carbon monoxide of at least major portion in the raw produce stream of (sour shift) described methane rich, to produce the raw produce stream of the hydrogen rich gas that comprises hydrogen, methane, carbonic acid gas, hydrogen sulfide and optional carbon monoxide;

(f) from the raw produce stream of described hydrogen rich gas, remove the carbonic acid gas of substantial part and the hydrogen sulfide of substantial part, with the raw produce stream from described hydrogen rich gas, produce the processed gas stream of hydrogen, methane and the carbon monoxide (if existence) that comprise substantial part;

(g), from described processed gas flow point from the hydrogen of major portion at least, with the processed gas of producing the hydrogen-depleted gas that (1) hydrogen product stream and (2) comprise methane, carbon monoxide (if existing in described processed gas stream) and optional hydrogen, flow;

(h) optionally make the processed gas stream of hydrogen-depleted gas be divided into stream of recycled gases and methane rich product gas stream;

(i) to the processed gas stream of the hydrogen-depleted gas of partial oxidation reactor supply at least a portion (or stream of recycled gases, if existed) and the second oxygen enriched gas stream; With

(j) make processed gas stream (or the stream of recycled gases of supply of supplied hydrogen-depleted gas, if existed) react in partial oxidation reactor with oxygen, to produce heat energy and feed gas stream, wherein said feed gas stream comprises carbon monoxide, hydrogen and steam

Wherein the described reaction in step (b) has synthetic gas demand, and be fed to processed gas stream (or the stream of recycled gases of the hydrogen-depleted gas of described partial oxidation reactor, if exist) amount be at least enough to produce enough carbon monoxide and hydrogen in described feed gas stream, at least to meet the synthetic gas demand of the described reaction in step (b).

Method of the present invention can be used for for example by different carbon raw materials, producing hydrogen.Described method also optionally can be used for production methane byproduct stream, particularly a kind of " pipeline-quality Sweet natural gas ".

In one embodiment, by being incorporated in the second heat exchanger unit from the feed gas stream of partial oxidation reactor, to remove heat energy from feed gas stream, subsequently feed gas stream is fed to hydrogenation methanator.

In one embodiment, there is step (h).In this case, if methane rich product (methane-rich product) gas stream comprises carbon monoxide, optionally make carbon monoxide under methanation catalyst exists, react product (methane-enriched product) gas stream to produce methane rich with the hydrogen in methane rich product gas stream.If the quantity not sufficient of the hydrogen in methane rich product gas stream with all in fact reaction of carbon monoxide that exist, a part of processed gas flow point can be driveed with side cross Hydrogen Separation step and and methane rich product gas stream recombine so that essential hydrogen to be provided.Or, can be by a part of hydrogen product stream and methane rich product gas stream recombine so that essential hydrogen to be provided.

When there is catalytic production of methane step (by methane rich product gas stream catalytic production of methane), optionally the product gas stream of the methane rich obtaining is introduced to the 3rd heat exchanger unit and remove heat energy with the product gas stream from methane rich.

Desirably, described methane rich product gas stream (or the product gas stream of described methane rich, if existed) be pipeline-quality Sweet natural gas.

In another embodiment, there is not step (h) and the processed gas stream of the hydrogen-depleted gas of substantial part is at least fed to partial oxidation reactor.

In another embodiment, the raw produce stream (from sour conversion unit) of the hydrogen rich gas from step (e) is incorporated into the 4th heat exchanger unit, with the raw produce stream from described hydrogen rich gas, remove heat energy, subsequently the raw produce stream of described hydrogen rich gas is fed to step (f) (acid gas removal unit).

In another embodiment, by producing one or more process vapour streams and/or being recovered in the heat energy of removing in first, second (if existence), the 3rd (if existence) and the 4th (if existence) heat exchanger unit by heating/overheated one or more process flow.For example, the heat energy reclaiming in First Heat Exchanger unit can be used for flow of superheated steam, is incorporated into subsequently in hydrogenation methanator, and/or produces the first process vapour stream; In the second heat exchanger unit (if exist), the heat energy of recovery can be used for producing the second process vapour stream, and/or overheated second or another process vapour stream; The heat energy reclaiming in the 3rd heat exchanger unit (if existence) can be used for producing the 3rd process vapour stream; Can be used for preboiler feed water with the heat energy reclaiming in the 4th heat exchanger unit (if existence), this boiler feed water is for the one or more middle production process steam at for example first, second, and third heat exchanger unit, and/or the raw produce of overheated cooling methane rich stream, be incorporated into subsequently step (e) (entering sour conversion unit).

Desirably, vapour stream is comprised of the one or more process vapour streams of at least a portion in fact, and described process vapour stream is produced by the process heat recuperation in first, second (if existence) and the 3rd (if existence) heat exchanger unit.

In another embodiment, the described reaction in step (b) has steam demand, synthetic gas demand and heat demand.

In one embodiment, about steam demand, (1) carbon raw material optionally comprises moisture content, (2) first oxygen enriched gas streams, if existed, optionally comprise steam, and (3) described vapour stream, the moisture content (if existence) that is included in the steam in described feed gas stream, described carbon raw material and the steam in described the first oxygen enriched gas stream (if existence) meet in fact described steam demand.

In one embodiment, about heat demand, the vapour stream and the feed gas stream that are fed to hydrogenation methanator comprise heat energy, and described heat energy combines is enough at least meet the heat demand of the described reaction in step (b).

In one embodiment, about synthetic gas demand, the carbon monoxide producing in POx reactor and the amount of hydrogen exceed the synthetic gas demand of hydrogenation methanation reaction, and by a part of feed gas diverting flow and with the raw produce gas stream of methane rich, merge before in step (e).

Another specific embodiment is that wherein said method is the embodiment of continuation method, wherein above-mentioned steps a-g and i-k (and h, if exist) operation in a continuous manner.

Another specific embodiment is wherein by the first oxygen enriched gas stream periodically or supply to the embodiment of hydrogenation methanator.The amount of the oxygen providing can be used as process control and becomes, for example, and for helping to be controlled at the temperature of hydrogenation methanator.Owing to providing a supply of oxygen in hydrogenation methanator, for example, from carbon (in the by product charcoal) partial oxidation/burning of raw material, to produce heat energy (and the carbon monoxide of a tittle and hydrogen).The amount that is fed to the oxygen of hydrogenation methanator can improve or reduce, and to improve the amount of the carbon being consumed, and therefore improves the amount at the heat energy of hydrogenation methanator situ generation.In this case, the heat energy that this original position produces is reduced in the heat demand of the described reaction in step (b), and therefore reduces the amount of the heat energy of supplying in vapour stream and feed gas stream in order to meet heat demand.

Another specific embodiment is wherein by the first oxygen enriched gas stream periodically or supply to the embodiment of hydrogenation methanator, the first oxygen enriched gas stream comprises steam, and the steam in described the first oxygen enriched gas stream is comprised of the one or more process vapour streams of at least a portion in fact.

Another specific embodiment is for wherein existing superheater with overheated feed gas stream, vapour stream or both, be fed to subsequently the embodiment of hydrogenation methanator, and superheater is by processed gas stream (or the methane-rich gas product flow (if existence) of a part of hydrogen-depleted gas, or stream of recycled gases (if existence), or the product gas stream of methane rich (if existence)) burning.

Another specific embodiment, for wherein vapour stream and feed gas stream being merged, is fed to the embodiment of hydrogenation methanator subsequently.

Another specific embodiment is the embodiment that wherein produces charcoal by product in step (b), wherein charcoal by product periodically or is continuously taken out from hydrogenation methanator, and the by product charcoal that at least a portion is taken out is provided to catalyst recovery operation.Subsequently by the catalyst recycle having reclaimed and with supplementary (makeup) catalyst combination, to meet the demand of hydrogenation methanation reaction.

Another specific embodiment is following embodiment, wherein in step (b), produce charcoal by product, hydrogenation methanator comprises the collecting region of wherein collecting charcoal by product, the first oxygen enriched gas stream is fed to hydrogenation methanator, and the first oxygen enriched gas stream is incorporated into the charcoal by product collecting region of hydrogenation methanator.Because by product charcoal comprises the carbon content from carbon raw material, expect that charcoal carbon preferentially consumes, to produce heat energy (with carbon monoxide and the hydrogen of a tittle).

Another specific embodiment is wherein under the pressure higher than hydrogenation methanator pressure, to produce the embodiment from the process vapour stream of described first, second (when existing) and the 3rd (when existing) heat exchanger unit.The pressure of process vapour stream (with final vapour stream) should be enough high, exceedes the pressure in hydrogenation methanator, makes not need other compression.

Reading by the following detailed description, those of ordinary skills will be easier to understand these and other embodiment of the present invention, feature and advantage.

Accompanying drawing summary

Fig. 1 is according to the chart of an embodiment of hydrogenation methanation method of the present invention, by described embodiment, from carbon raw material production hydrogen product stream and optional methane product, is flowed.

Fig. 2 is the chart of the fore-end of the hydrogenation methanation method of the raw produce stream of wherein production methane rich.

Fig. 3 is the chart that the raw produce for further processing methane rich flows to produce the method that hydrogen product stream and optional methane product flow.

Detailed Description Of The Invention

The disclosure relates to the method that carbon raw material is changed into multiple gaseous product and produce hydrogen product stream, and described method comprises except other step: to hydrogenation methanator, provide carbon raw material, hydrogenation methanation catalyst, synthetic gas incoming flow and vapour stream carbon raw material is converted into multiple gaseous product in the presence of hydrogenation methanation catalyst, carbon monoxide, hydrogen and steam.Synthetic gas incoming flow is by the supply of partial oxidation (POx) reactor, and described reactor consumes at least a portion methane production of hydrogenation methanation reaction for the synthesis of gas and heat generation.Then process described multiple gaseous product finally to obtain hydrogen product stream, and optional methane product stream.Methane product stream (if existence) expects to have enough purity, to have the qualification of " pipeline-quality Sweet natural gas ".

The present invention can be combined in disclosed theme in the following patent of owning together and implement: US2007/0000177A1, US2007/0083072A1, US2007/0277437A1, US2009/0048476A1, US2009/0090056A1, US2009/0090055A1, US2009/0165383A1, US2009/0166588A1, US2009/0165379A1, US2009/0170968A1, US2009/0165380A1, US2009/0165381A1, US2009/0165361A1, US2009/0165382A1, US2009/0169449A1, US2009/0169448A1, US2009/0165376A1, US2009/0165384A1, US2009/0217582A1, US2009/0260287A1, US2009/0220406A1, US2009/0217590A1, US2009/0217586A1, US2009/0217588A1, US2009/0218424A1, US2009/0217589A1, US2009/0217575A1, US2009/0229182A1, US2009/0217587A1, US2009/0259080A1, US2009/0246120A1, US2009/0324458A1, US2009/0324459A1, US2009/0324460A1, US2009/0324461A1, US2009/0324462A1, US2010/0076235A1 and WO2010/033846A2.

In addition, the present invention can be combined in the U.S. Patent Application Serial Number 12/648 of owning together, 469 (the reel number FN-0044 US NP1 of agency, be entitled as PROCESS FOR PREPARING A CATALYZED CARBONACEOUS FEEDSTOCK (for the preparation of the method for the carbon raw material of catalysis)) and 12/648, 471 (the reel number FN-0045 US NP1 of agency, be entitled as PROCESS FOR PREPARING A CATALYZED CARBONACEOUS FEEDSTOCK (for the preparation of the method for the carbon raw material of catalysis)), they are submitted on December 29th, 2009 separately, with 12/778,548 (the reel number FN-0048 US PRV of agency, be entitled as PROCESSES FOR HYDROMETHANATION OF A CARBONACEOUS FEEDSTOCK (for the method for the hydrogenation methanation of carbon raw material), on May 12nd, 2010 submits to) in disclosed theme implement.

All publications, patent application, patent and other reference mentioned herein (include but not limited to above referenced those, if not in addition explanation) clear and definite entirety is by reference incorporated to herein for all objects, just looks like that abundant description is the same.

Unless otherwise defined, otherwise all technology used herein and scientific terminology have common the understood identical implication of disclosure one skilled in the art.The in the situation that of conflict, with this specification sheets (comprising definition), be as the criterion.

Unless clearly demonstrate, otherwise trade mark represented with subscript.

Although can be used for enforcement of the present disclosure or test with those method and materials similar or that be equal to described herein, this paper describes suitable method and material.

Unless otherwise indicated, otherwise all per-cent, part, ratio etc. by weight.

Equivalent, concentration or other value or parameter be as scope, or enumerating of upper and lower bound value and while providing, be interpreted as specifically disclosing all scopes that formed by any paired any upper and lower bound scope limit, and no matter whether disclose separately scope.When enumerating numerical range herein, unless otherwise indicated, otherwise this scope is intended to comprise its end points and all integers and mark within the scope of this.When limited range, be not intended to the occurrence that the scope of the present disclosure is confined to enumerate.

When term " about " is used for the end points of the value of description or scope, the disclosure is understood to include the concrete value or the end points that relate to.

Term used herein " comprises ", " comprising ", " comprising ", " comprising ", " having ", " having " or their any other variant, is intended to contain nonexcludability and comprises.For example, process, method, goods or the equipment that comprises the key element of enumerating needn't only be confined to those key elements, but can comprise and clearly not enumerating or other key element that these processes, method, goods or equipment are intrinsic.In addition, unless clear and definite contrary explanation, "or" refers to the "or" of comprising property rather than the "or" of exclusiveness.For example, any one of following A or B:A of satisfying condition is that true (or existence) and B are vacation (or not existing), A is that false (or not existing) and B are true (or existence), and A and B are true (or existence).

Use " one " to describe different key elements herein and assembly only for convenient and provide common implication of the present disclosure.This description should be regarded as and comprise one or at least one, unless and obviously refer else, otherwise odd number also comprises plural number.

Unless otherwise defined herein, otherwise term used herein " substantial part " refers to the material of mentioning that is greater than approximately 90%, is preferably greater than approximately 95% the material of mentioning, more preferably greater than approximately 97% the material of mentioning.When relating to molecule (such as methane, carbonic acid gas, carbon monoxide and hydrogen sulfide), per-cent based on mole, and other is based on weight (such as the carbonaceous fines for carrying secretly).

Unless otherwise defined herein, otherwise term used herein " major portion " refers to the material of mentioning that is greater than approximately 50%.When relating to molecule (such as methane, carbonic acid gas, carbon monoxide and hydrogen sulfide), per-cent based on mole, and other is based on weight (such as the carbonaceous fines for carrying secretly).

Term used herein " carbonaceous material " can be for example biomass defined herein and abiotic material.

Term used herein " biomass " refers to by recently the derivative carbonaceous material of organism of (for example, in the past 100 years in) survival, comprises the biomass based on plant and the biomass based on animal.In order to clarify, biomass do not comprise the carbonaceous material based on fossil, such as coal.For example,, referring to the US2009/0217575A1 being incorporated to above, US2009/0229182A1 and US2009/0217587A1.

Term used herein " based on the biomass of plant " refers to the material derived from green plants, farm crop, algae and tree, such as, but be not limited to, sweet sorghum, bagasse, sugarcane, bamboo, hybridization white poplar, willow, acacia, eucalyptus, clover, trifolium, oil palm, switchgrass, arabian cron, broomcorn millet, manioca and spire awns (for example, huge awns (Miscanthus x giganteus)).Biomass also comprise the refuse from agricultural tillage, processing and/or degraded, such as corn cob and corn husk, maize straw, straw, nutshell, vegetables oil, Semen Brassicae Campestris oil, rapeseed oil, biofuel, bark, wood chip, sawdust and garden refuse.

Term used herein " based on the biomass of animal " refers to by animal cultivation and/or utilizes the refuse producing.For example, biomass include, but not limited to the refuse from livestock culturing and processing, for example, such as Animal manure, birds droppings, poultry garbage, animal tallow and municipal solid waste (, dirt).

Term used herein " abiotic matter " refers to those carbonaceous materials that do not comprised by term defined herein " biomass ".For example, abiotic matter includes, but not limited to hard coal, bituminous coals, inferior-bituminous coals, brown coal, petroleum coke, asphaltene, liquid petroleum resistates or their mixture.For example,, referring to the US2009/0166588A1 being incorporated to above, US2009/0165379A1, US2009/0165380A1, US2009/0165361A1, US2009/0217590A1 and US2009/0217586A1.

Term used herein " petroleum coke (petroleum coke) " and " petroleum coke (petcoke) " comprise the solid thermal decomposed product (heavy residue-" Residual oil petroleum coke ") of the high boiling hydrocarbon fraction that (i) obtain in petrolize; (ii) process tar sand solid thermal decomposed product (bituminous matter is husky or oil is husky-" tar sand petroleum coke ") both.These carbonated product comprise, for example, and raw, calcining, needle-like and fluidized-bed petroleum coke.

Residual oil petroleum coke also can be derived from crude oil, for example, and by the coking method for making the upgrading of heavy-gravity irreducible oil, described petroleum coke contains ash content as compared with small component, be generally approximately 1.0 % by weight or still less, be more typically approximately 0.5 % by weight or still less, based on the weight of coke.Conventionally, this lower-ash content in ash content coke comprises metal, such as nickel and vanadium.

Tar sand petroleum coke can be husky derived from oil, for example, by the coking method for making the husky upgrading of oil.Tar sand petroleum coke contains ash content as compared with small component, conventionally, within the scope of approximately 2 % by weight-Yue 12 % by weight, is more typically within the scope of approximately 4 % by weight-Yue 12 % by weight, based on the gross weight of tar sand petroleum coke.Conventionally, this higher-ash content in ash content coke comprises the material such as silicon-dioxide and/or aluminum oxide.

Petroleum coke has intrinsic low moisture content, conventionally, and within the scope of about 0.2-approximately 2 % by weight (based on the gross weight of petroleum coke); It also has low-down water saturates ability conventionally, to allow conventional catalyst soakage method.

Petroleum coke can comprise at least about 70 % by weight carbon, at least about 80 % by weight carbon, or at least about 90 % by weight carbon, based on the gross weight of petroleum coke.Conventionally, petroleum coke comprises and is less than approximately 20 % by weight mineral compound, based on the weight of petroleum coke.

Term used herein " bituminous matter " is at room temperature aromatics carbon solid, and can be derived from the processing of for example crude oil and crude oil tar sand.

Term used herein " coal " refers to mud coal, brown coal, inferior-bituminous coals, bituminous coals, hard coal or their mixture.In certain embodiments, the carbon content of coal is less than approximately 85%, or is less than approximately 80%, or is less than approximately 75%, or is less than approximately 70%, or is less than approximately 65%, or is less than approximately 60%, or is less than approximately 55%, or is less than approximately 50 % by weight, based on the gross weight of coal.In other embodiments, the carbon content scope of coal is the highest by approximately 85%, or the highest by approximately 80%, or the highest approximately 75 % by weight, based on the gross weight of coal.The example of available coal includes, but not limited to Illinois #6, Pittsburgh #8, Beulah (ND), Utah Blind Canyon and Powder River Basin (PRB) coal.Hard coal, bituminous coals, inferior-bituminous coals and brown coal respectively can be containing having an appointment 10 % by weight, about 5-approximately 7 % by weight, and about 4-approximately 8 % by weight and about 9-approximately 11 % by weight ash contents, by butt coal gross weight.But the ash oontent in any concrete coal source depends on grade and the source of coal, as those skilled in the art are familiar with.Referring to for example " Coal Data:A Reference (coal data refer) ", Energy Information Administration (energy information management department), Office of Coal, Nuclear, Electric and Alternate Fuels (coal, core, electricity and substitute energy office), U.S.Department of Energy (USDOE), DOE/EIA-0064 (93), February nineteen ninety-five.

The ash content being produced by burning of coal comprises flying dust and bottom ash conventionally, as those skilled in the art are familiar with.From the flying dust of bituminous coals, can comprise about 20-approximately 60 % by weight silicon-dioxide and about 5-approximately 35 % by weight aluminum oxide, based on the gross weight of flying dust.From the flying dust of inferior-bituminous coals, can comprise about 40-approximately 60 % by weight silicon-dioxide and about 20-approximately 30 % by weight aluminum oxide, based on the gross weight of flying dust.From the flying dust of brown coal, can comprise about 15-approximately 45 % by weight silicon-dioxide and about 20-approximately 25 % by weight aluminum oxide, based on the gross weight of flying dust.Referring to people such as such as Meyers, " Fly Ash.A Highway Construction Material (flying dust-highway structure material); " Federal Highway Administration (Federal Highway Administration), report FHWA-IP-76-16, Washington., DC, 1976.

From the bottom ash of bituminous coals, can comprise about 40-approximately 60 % by weight silicon-dioxide and about 20-approximately 30 % by weight aluminum oxide, based on the gross weight of bottom ash.From the bottom ash of inferior-bituminous coals, can comprise about 40-approximately 50 % by weight silicon-dioxide and about 15-approximately 25 % by weight aluminum oxide, based on the gross weight of bottom ash.From the bottom ash of brown coal, can comprise about 30-approximately 80 % by weight silicon-dioxide and about 10-approximately 20 % by weight aluminum oxide, based on the gross weight of bottom ash.Referring to for example Moulton, Lyle K. " Bottom Ash and Boiler Slag (bottom ash and boiler slag); " Proceedings of the Third International Ash Utilization Symposium (the international ash utilization discussion of San Jie summary), U.S.Bureau of Mines (United States Bureau of Mines), information announcement numbers 8640, Washington., DC, 1973.

Term " unit " refers to unit operation.When description exists more than one " unit ", those unit operate in parallel.But based on context, single " unit " can comprise the unit of more than one serial or parallel connection.For example, acid gas removal unit can comprise hydrogen sulfide removal unit, the co 2 removal unit of then connecting.As another example, contaminant trace species removal unit can comprise the first removal unit for the first contaminant trace species, and then series connection is for the second removal unit of the second contaminant trace species.As another example, methane compressor unit can comprise the first methane compressor with compressed methane product flow to the first pressure, and second methane compressor of then connecting is with further compressed methane product flow to the second (higher) pressure.

Term " synthetic gas demand " refers to and in hydrogenation methanator, keeps synthetic gas balance.As discussed above, in the stable state hydrogenation methanation reaction of total expectation (referring to above equation (I), (II) and (III)), hydrogen and carbon monoxide produce and consume in balance.Because hydrogen and carbon monoxide all take out as a part of gaseous product, hydrogen and carbon monoxide must be joined in (and/or optional independent original position generation of oxygen of using supply by burning/oxidizing reaction) hydrogenation methanator, its amount is at least and keeps this molecular balance required.The amount that for purposes of the present invention, must join hydrogen in hydrogenation methanator and carbon monoxide is " synthetic gas demand " (getting rid of independent original position synthetic gas produces).

Term " steam demand " refers to the amount that must join the steam in hydrogenation methanator.Steam consumes in hydrogenation methanation reaction, and must join in hydrogenation methanator.The theory consumption of steam is 2 moles of carbon in 2 moles/charging, to produce the methane of 1 mole and the carbonic acid gas of 1 mole (referring to equation formula V).In actual practice, steam consumption is imperfect effectively, and steam is taken out together with product gas; Therefore, the steam that is greater than theoretical amount need to be joined to hydrogenation methanator, this amount is " steam demand ".Steam can add by the steam in for example vapour stream, feed gas stream, the steam (if existence) in the first oxygen enriched gas stream and the steam being produced by any moisture content original position of carbon raw material.The amount (and source) of steam to be added is further discussing in detail below.It should be noted that, any steam that original position produces or is fed in hydrogenation methanator at the temperature lower than hydrogenation methanation reaction temperature has impact to " heat demand " of hydrogenation methanation reaction.

Term " heat demand " refers to the amount of the reaction to keep step (b) in thermally equilibrated heat energy that must join in hydrogenation methanator, further discusses in detail as discussed above and below.

Material, method and embodiment be herein only for illustrating, unless illustrate, otherwise be not intended to for restricted.

general process information

In one embodiment of the invention, can produce hydrogen product stream (85) by carbon raw material, as illustrated in Fig. 1-3.

With reference to figure 1, carbon raw material (32), hydrogenation methanation catalyst (31), the feed gas stream (20) that comprises carbon monoxide, hydrogen and steam and vapour stream (25) are provided to hydrogenation methanator (200).The optionally same hydrogenation methanator (200) that is fed to of oxygen enriched gas stream (15a) (such as the oxygen of purifying, optionally mixing with steam (16)).Under hydrogenation methanation catalyst exists, under pressure and temperature condition suitable, carbon raw material, carbon monoxide, hydrogen, steam and optional oxygen react in hydrogenation methanator (200), to form the raw produce stream (50) of methane rich, this raw produce stream (50) comprises methane, hydrogen and multiple other gaseous product, generally include carbonic acid gas and carbon monoxide, and steam and some pollutent (such as hydrogen sulfide and ammonia), this depends primarily on the concrete raw material of utilization.Also conventionally form charcoal by product (52), and periodically or continuously take out from hydrogenation methanator (200).

As shown in Figure 2, carbon raw material (32) is derived from one or more carbonaceous materials (10), described carbonaceous material (10) processing in raw material preparation part (190) as discussed below.

Hydrogenation methanation catalyst (31) can comprise one or more catalyzer thing classes (specy), as discussed below.

Carbon raw material (32) and hydrogenation methanation catalyst (31) can mix (that is, so that the carbon raw material of catalysis to be provided) closely, are provided to subsequently hydrogenation methanator (200), as discussed below.

As shown in Figure 1, by the partial oxidation of stream of recycled gases (sometimes flowing also referred to as the processed gas of hydrogen-depleted gas) (30), in partial oxidation (POx) reactor (100), produce feed gas stream (20), as discussed below.Stream of recycled gases (30) mainly comprises methane and optional carbon monoxide and/or hydrogen, and this depends on the processing of the raw produce gas stream (50) of methane rich, as discussed below.The second oxygen-rich stream (15) is fed to POx reactor (100), the POx reaction obtaining produces at least one carbonoxide, hydrogen and some steam, and therefore feed gas stream (20) mainly comprises other gaseous component (such as carbonic acid gas) of carbon monoxide, hydrogen and steam and optional small amount.Can as required steam be joined to feed gas stream (20), for example by vapour stream (25) (for example, by vapour stream (25a) and (25b) (Fig. 2)), to meet the steam demand of hydrogenation methanation reaction, as discussed further below.Feed gas stream (20) can need cooling when it leaves POx reactor (100), is fed to subsequently in hydrogenation methanator (200), and this can realize by First Heat Exchanger unit (140).The heat energy reclaiming in First Heat Exchanger unit (140) can be for example for generation of process steam and overheated other process flow, as discussed further below.

The raw produce stream (50) of the methane rich being produced by hydrogenation methanation reaction is taken out from hydrogenation methanator (200), in sour conversion reactor (700), stand subsequently acid and transform, to improve hydrogen content and to produce the raw produce stream (72) of hydrogen rich gas.Conventionally, at sour conversion reactor (700) before, by first cooling in the second heat exchanger unit (400) the raw produce stream (50) of methane rich, to produce cooling raw produce stream (70), be fed to subsequently sour conversion reactor (700).The heat energy reclaiming in the second heat exchanger unit (400) can be for example for generation of process steam and overheated other process flow, as discussed further below.

If the carbon monoxide producing in POx reactor (100) and hydrogen exceed the synthetic gas demand of hydrogenation methanation reaction, as discussed below, can pass through by-pass line (21) and merge by a part of feed gas stream (20) shunting and with cooling raw produce gas stream (70), for being fed to sour conversion unit (700).

With aftertreatment, leave the raw produce stream (72) of the hydrogen rich gas of sour conversion reactor (700), to remove acid gas (CO in acid gas removal unit (800) ₂and H ₂s), to produce the processed gas stream (80) that comprises methane, hydrogen and optional carbon monoxide.Can be by independent H ₂s flows (78) and CO ₂stream (79) is removed from acid gas removal unit (800), for further processing/using, as discussed below.

Processed gas stream (80) is fed to hydrogen separation unit (850), to produce the processed gas stream (82) of hydrogen product stream (85) and hydrogen-depleted gas.Desirably, produce high-purity hydrogen product (about 99mol% or larger).

The processed gas stream (82) of hydrogen-depleted gas comprises in fact methane conventionally, but can optionally contain other gases such as carbon monoxide and hydrogen, and this depends on the operation of sour conversion unit (700) and hydrogen separation unit (850).The processed gas stream (82) of hydrogen-depleted gas can be used as stream of recycled gases (30) like this.

In some embodiments, can be by the gas stream of hydrogen-depleted gas (82) shunting to produce stream of recycled gases (30) and methane rich product gas stream (95).If the gas stream of hydrogen-depleted gas (82) contains carbon monoxide, can it be further purified/process for example arranging in methanation unit (950), to produce the product gas stream (97) of methane rich.If expected, can improve by using acid to transform by-pass line (71) carbon monoxide content of the gas stream (82) of hydrogen-depleted gas, for other methane production (take hydrogen gas production as cost), this acid transforms by-pass line (71) and walks around sour conversion unit (700) by other the raw produce stream (70) of methane rich cooling part mistake, to preserve carbon monoxide content (otherwise it may be consumed).

If the hydrogen content of the gas stream of hydrogen-depleted gas (82) be not enough to the gas stream (82) of hydrogen-depleted gas in all in fact reaction of carbon monoxide of existing, can a part of processed gas flow to (80) (it contains hydrogen) takes out by by-pass line (86) and and the processed gas of hydrogen-depleted gas flow (82) combination so that essential hydrogen to be provided.Part hydrogen product stream (85) also can be used for this object.

Described optional methane product steam (99) can be finally for example the product gas stream (97) of methane rich product gas stream (95) and/or methane rich.

The methane product stream of desired type is pipeline-quality Sweet natural gas, as described further below.

Other optional gas processing step can occur before or after acid gas removal unit (800).

The vapour stream (25) that is fed to hydrogenation methanator (200) is expected derived from producing and overheated steam by one or more process heat recuperation operations, for example, one or more from interchanger (140), (400), (401) and (403), as Figure 1-3.

Result is to produce the hydrogenation methanation method that hydrogen product stream and optional methane product flow, and it can be at least self-sufficient and integrated steam, heat and synthetic gas under steady state operation, as discussed further below.

hydrogenation methanator/reaction

Any polytype gasifying reactor can be used for hydrogenation methanator (200).Suitable reactor comprises those with reaction chamber, and described reaction chamber is adverse current fixed bed, co-current flow fixed bed, fluidized-bed or folder stream (entrained flow) or moving bed reaction chamber.

Hydrogenation methanator (200) is generally fluidized-bed reactor.Hydrogenation methanator (200) can be for example " flowing downward " counterflow configuration, wherein at higher point, introduce carbon raw material (32), make particle flow downward to charcoal by product collecting region along fluidized-bed, and gas flows with upward direction, and is removed at the point higher than fluidized-bed.Or hydrogenation methanator (200) can be " upwards flowing " flow structure, wherein at lower some feed carbon raw material (32), makes particle travel up to charcoal by product collecting region along fluidized-bed together with gas.Conventionally, in " upwards flowing " structure, in the bottom of reactor, also there is collecting region, for the larger particle (comprising charcoal) not being fluidized.

Step (b) occurs in hydrogenation methanator (200).

When oxygen enriched gas stream (15a) is also fed to hydrogenation methanator (200), a part also can be consumed from the carbon content of carbon raw material in oxidation/combustion reactions, produces heat energy and carbon monoxide and hydrogen.Hydrogenation methanation and oxidation/combustion reactions can occur simultaneously.According to the structure of hydrogenation methanator (200), as discussed below, these two steps can occur in region identical in reactor, or mainly in Yi Ge district, occur.For example, when oxygen enriched gas stream (15a) being fed to the region of the hydrogenation methanator (200) of collecting charcoal by product, such as lower than active hydrogenation methanation fluidised bed zones, hydrogenation methanation reaction will be mainly in hydrogenation methanation fluidised bed zones, and partial oxidation/combustion reactions will be mainly at charcoal by product collecting zone.

Hydrogenation methanator (200) operates conventionally under the high pressure and temperature of appropriateness, need in the reaction chamber of reactor, introduce suitable carbon raw material, keeps the required temperature of raw material, pressure and flow velocity simultaneously.Those skilled in the art are familiar with feed entrance, so that carbon raw material is supplied in the reaction chamber with high pressure and/or hot environment, comprise tar feeder, screw feeder, rotory piston and locking hopper.It should be understood that feed entrance can comprise two or more pressure-balancing components, such as locking hopper, they can be used alternatingly.In some cases, can under the pressure condition of working pressure that exceedes reactor, prepare carbon raw material, therefore, microparticle compositions can directly pass in reactor, without further pressurization.

Hydrogenation methanator (200) is desirably under appropriate temperature and pressure and operates, temperature is at least about 700 ℉ (approximately 371 ℃), or at least about 800 ℉ (approximately 427 ℃), or at least about 900 ℉ (approximately 482 ℃), to approximately 1500 ℉ (approximately 816 ℃), or to approximately 1400 ℉ (approximately 760 ℃), or to approximately 1300 ℉ (704 ℃); Pressure is about 250psig (about 1825kPa, absolute pressure), or about 400psig (about 2860kPa), or about 450psig (about 3204kPa), or about 500psig (about 3549kPa), to about 800psig (about 5617kPa), or to about 700psig (about 4928kPa), or to about 600psig (about 4238kPa).

In hydrogenation methanator (200), typical gas flow rates is from approximately 0.5 feet per second clock (about 0.15m/ second), or from approximately 1 feet per second clock (about 0.3m/ second), to approximately 2.0 feet per second clocks (about 0.6m/ second), or to approximately 1.5 feet per second clocks (about 0.45m/ second).

Hydrogenation methanation reaction has steam demand, heat demand and synthetic gas demand.These conditional combinations get up for being identified for the important factor of operational condition of hydrogenation methanation reaction and all the other processes.

For example, the steam demand of hydrogenation methanation reaction needs the mol ratio of steam and carbon (in raw material) to be at least about 1.But mol ratio is greater than approximately 1 conventionally, or from approximately 1.5 (or larger), to approximately 6 (or still less), or to approximately 5 (or still less), or to approximately 4 (or still less), or to approximately 3 (or still less), or to approximately 2 (or still less).The moisture content of carbon raw material (32), and the steam being included in feed gas stream (20) and oxygen enriched gas stream (15a) (if existence) will determine the amount of the vapour stream (25) that joins hydrogenation methanator (200).In one embodiment of the invention, vapour stream (25) meets the steam demand of hydrogenation methanation reaction, and this has considered the moisture content and the steam (Fig. 2) being included in feed gas stream (20) and the first oxygen enriched gas stream (15a) (if existence) of carbon raw material (32).

Also described above, hydrogenation methanation reaction is essentially thermally equilibrated, but for example, due to process calorific loss and other energy requirement (, the evaporation of the moisture in raw material), some heats must be fed to hydrogenation methanation reaction to keep thermal equilibrium (heat demand).Add vapour stream (25) and feed gas stream (20), add the oxygen that is incorporated into hydrogenation methanator (200) from the first oxygen enriched gas stream (15a) exists, optional partial combustion/the oxidation of carbon (from carbon raw material), should be enough to meet the heat demand of hydrogenation methanation reaction.

When utilizing, oxygen enriched gas stream (15a) can be fed to hydrogenation methanator (200) by any suitable mode, such as oxygen, oxygen-air mixture, oxygen-vapour mixture or the oxygen-noble gas mixtures of direct injection purifying in reactor.Referring to the such as people such as US4243639 and Chiaramonte, Hydrocarbon Processing (hydrocarbon processing), September nineteen eighty-two, 255-257 page.Oxygen enriched gas stream (15a) produces by standard air-isolation technique conventionally, and usually used as high purity oxygen air-flow (approximately 95% or more volume percentage of oxygen, butt) charging.

When providing, oxygen enriched gas stream (15a) is usually used as providing with the mixture of vapour stream (16), and introduce under following temperature and pressure, temperature is from approximately 400 ℉ (approximately 204 ℃), or from approximately 450 ℉ (approximately 232 ℃), or from approximately 500 ℉ (approximately 260 ℃), to approximately 750 ℉ (approximately 399 ℃), or to approximately 700 ℉ (approximately 371 ℃), or to approximately 650 ℉ (approximately 343 ℃), at least a little higher than pressure existing in hydrogenation methanator (200) of pressure.

Oxygen enriched gas stream (15a) also can be used as with the mixture of vapour stream (25) and introduces.

When providing, oxygen enriched gas stream (15a) is introduced at the point of the fluidised bed zones lower than hydrogenation methanator (200) conventionally, to avoid forming focus in reactor, and avoids the burning of gaseous product.Can for example oxygen enriched gas stream (15a) be advantageously incorporated into the region of the hydrogenation methanator (200) of collecting by product charcoal, described region is conventionally in the bottom of reactor, make compared with the carbon with in more active hydrogenation methanation region, the carbon in by product charcoal is preferentially consumed.

The amount that changes the oxygen that is fed to hydrogenation methanator (200) provides favourable process control.The amount that improves oxygen will improve oxidation/burning, and therefore improve original position heat generation.The amount that reduces oxygen will reduce original position heat generation on the contrary.

In hydrogenation methanator (200), for the gas that makes carbon raw material (32) pressurization and reaction, comprise vapour stream (25), such as argon gas combines, it can be fed to hydrogenation methanator (200) according to method known to those skilled in the art (such as what above oxygen enriched gas stream (15a) is discussed) with feed gas stream (20) and optional other steam, nitrogen, air or rare gas element.Result is, vapour stream (25) and feed gas stream (20) must provide under higher pressure, and this makes them can enter hydrogenation methanator (200).

For example, by control, be fed to the vapour stream (25) of hydrogenation methanator (200) and amount and the temperature of feed gas stream (20), and the amount of optional oxygen (as discussed above), can be controlled in the temperature in hydrogenation methanator (200).

Advantageously, steam for hydrogenation methanation reaction is produced (such as producing at waste heat boiler by the trapping of process heat by other process operation, be commonly referred to " process steam " or " steam of process-generation "), in some embodiments, only as the steam supply of process-generation.For example, can by by heat exchanger unit or waste heat boiler (such as, for example, (140a) in Fig. 2 and (400b), and/or (403) in Fig. 2 and 3) the process vapour stream (such as (25a), (25b) and (43)) that produces is fed to hydrogenation methanator (200).

In certain embodiments, described herein for generation of steam neutrality on total process nature of hydrogen product stream (85), make by meeting the steam demand (pressure and amount) of hydrogenation methanation reaction with the thermal exchange of the process heat of different steps wherein, or the steam positive, make to produce excessive steam and can be for example for generating.Desirably, the steam of process-generation account for hydrogenation methanation reaction steam demand be greater than approximately 95 % by weight, or be greater than approximately 97 % by weight, or be greater than approximately 99 % by weight, or approximately 100 % by weight or larger.

The result of hydrogenation methanation reaction is the raw produce stream (50) of methane rich, conventionally comprises CH ₄, CO ₂, H ₂, CO, H ₂s, unreacted steam, the fines of carrying secretly and optional other pollutent are such as NH ₃, COS, HCN and/or elemental mercury from vapor, this depends on the character for the carbonaceous material of hydrogenation methanation.

If hydrogenation methanation reaction is with synthetic gas balance movement, the raw produce stream (50) of methane rich conventionally comprises at least about 20mol% when leaving hydrogenation methanator (200), or at least about 25mol%, or at least about 27mol% methane, based on the mole number of methane, carbonic acid gas, carbon monoxide and hydrogen in the raw produce stream (50) of methane rich.In addition, the raw produce of methane rich stream (50) conventionally comprises at least about 50mol% methane and adds carbonic acid gas, based on the mole number of methane, carbonic acid gas, carbon monoxide and hydrogen in the raw produce stream (50) of methane rich.

If feed gas stream (20) contains higher than and exceed excessive carbon monoxide and/or the hydrogen of synthetic gas demand, to the molar percentage of methane and carbon dioxide in the raw produce stream of methane rich, can there are some dilution effects.But, conventionally from the excessive synthetic gas of POx reactor (100), produce and will from feed gas stream (20), separate and be fed to sour conversion reactor (700) (other over hydrogenation methanator (200)) by by-pass line (21), as discussed below.

pOx reactor (100)

The POx reactor that is applicable to being potentially combined with the present invention is that person of ordinary skill in the relevant is known under common implication, and comprise, for example, those reactors based on deriving from Royal Dutch Shell plc, Siemens AG, General Electric Company, Lurgi AG, Haldor Topsoe A/S, Uhde AG, KBR Inc. and other technology.Catalytic and non-catalytic POx reactor are all applicable to the present invention.In one embodiment, (heat) that POx reactor is non-catalytic.

Stream of recycled gases (30) and the second oxygen enriched gas stream (15) are fed to POx reactor (100) reaction.Oxidizing reaction is heat release, therefore under the temperature and pressure raising, produces obtained feed gas stream (20).POx reactor (100) is conventionally higher at least about 250 ℉ (at least about 139 ℃) than hydrogenation methanator (200), or at least about 350 ℉ (at least about 194 ℃), or at least about 450 ℉ (at least about 250 ℃), or operate at the temperature at least about 500 ℉ (at least about 278 ℃).Typical operating temperature range is from approximately 1800 ℉ (approximately 982 ℃), or from approximately 2000 ℉ (approximately 1093 ℃), or from approximately 2200 ℉ (approximately 1204 ℃), to approximately 2800 ℉ (approximately 1538 ℃), or to approximately 2500 ℉ (approximately 1371 ℃), or to approximately 2300 ℉ (approximately 1260 ℃).

POx reactor (100) also operates under than the high pressure of hydrogenation methanator (200), make feed gas stream (20) to be fed to hydrogenation methanator (200), and without other pressurization, even if there is intermediate treatment.Conventionally, the pressure of the pressure ratio in POx reactor (100) in hydrogenation methanator (200) is high at least about 50psi (about 345kPa), or at least about 100psi (about 690kPa).Typical working pressure scope is from about 400psig (about 2860kPa), or from about 500psig (about 3549kPa), or from about 550psig (about 3894kPa), to about 900psig (about 6307kPa), or to about 800psig (about 5617kPa), or to about 700psig (about 4928kPa), or to about 650psig (about 4583kPa).Under this pressure, operation can need recirculated compressed gas stream (30), is incorporated into subsequently POx reactor (100).

POx reaction is produced steam and other gas of carbon monoxide and hydrogen and small amount by the methane in stream of recycled gases (30).It is about 1.6-approximately 1.8 that POx reaction causes hydrogen and carbon monoxide mol ratio conventionally.If there is hydrogen and/or carbon monoxide in stream of recycled gases (30), can change a little this ratio.

If expected, the available other hydrogen make of feed gas stream (20), to improve mol ratio, for example, by hydrogen product stream (85) or by using by-pass line (86) to supplement.

For the temperature that makes feed gas stream (20) relaxes to the level that is suitable for being fed to hydrogenation methanator (200), feed gas stream (20) can be mixed with for example vapour stream of steam (25) (with flow of superheated steam (25)).Also steam can be fed directly to POx reactor (100).Or, or with above combination, can make feed gas stream (20) through First Heat Exchanger unit (140), to remove heat energy, be incorporated into subsequently in hydrogenation methanator (200).In one embodiment, as described in Figure 2, First Heat Exchanger unit (140) comprise steam boiler (140a), are then vapor superheater (140b).Can make the stream (39b) of boiler feed water through steam boiler (140a), to produce the first process vapour stream (65), make subsequently it through vapor superheater (140b), to produce the overheated process vapour stream (25b) with suitable temperature and pressure, for introduction into hydrogenation methanator (200), for example,, by mixing with feed gas stream (20).

other gas processing

Fines is removed

The hot gaseous effluent that leaves the reaction chamber of hydrogenation methanator (200) can pass through fines remover unit (not shown), described unit is incorporated to inside and/or the outside of hydrogenation methanator (200), and it is as abscission zone.Particle that will be too heavy and can not be left the gas entrainment of hydrogenation methanator (200) (, fines) be back to hydrogenation methanator (200), for example, be back to reaction chamber (for example, fluidized-bed).

The remaining fines of carrying secretly can be removed in fact, when needed, by any suitable device such as inside and/or external cyclone are then optionally Venturi scrubbers.Can process the fines of these recovery, to reclaim base metal catalysts, or directly raw material preparation is returned in recirculation, as described in the US2009/0217589A1 being incorporated to above.

The fines of removing " substantial part " refers to that from obtained gas stream, removing a certain amount of fines can not affect adversely downstream processing; Therefore, should remove at least fines of substantial part.The super-fine material of some less levels can be retained in obtained gas stream, and its degree can significantly not affect adversely downstream processing.Conventionally, remove at least about 90 % by weight, or at least about 95 % by weight, or be greater than approximately 20 μ m at least about the particle diameter of 98 % by weight, or be greater than approximately 10 μ m, or be greater than the fines of approximately 5 μ m.

Thermal exchange (400)

According to hydrogenation methanation condition, can produce and there is following temperature, the raw produce stream (50) of the methane rich of pressure and speed: temperature range is approximately 800 ℉ (approximately 427 ℃)-Yue 1500 ℉ (approximately 816 ℃), be more typically about 1100 ℉ (approximately 593 ℃)-Yue 1400 ℉ (approximately 760 ℃), pressure is about 50psig (about 446kPa)-Yue 800psig (about 5617kPa), be more typically about 400psig (about 2860kPa)-Yue 600psig (about 4238kPa), and speed is approximately 0.5 feet per second clock (about 0.15m/ second)-Yue 2.0 feet per second clocks (about 0.61m/ second), be more typically about 1.0 feet per second clocks (0.30m/ second)-Yue 1.5 feet per second clock (about 0.46m/ second).

Can for example the raw produce stream (50) of methane rich be provided to heat recovery unit, for example, the second heat exchanger unit (400), as shown in Figure 1.The second heat exchanger unit (400) flows from the raw produce of methane rich the temperature that (50) are removed at least a portion heat energy and reduced the raw produce stream (50) of methane rich, to produce the raw produce stream (70) of temperature lower than the cooling methane rich of the raw produce stream (50) of methane rich.The heat energy reclaiming by the second heat exchanger unit (400) can be used for producing the second process vapour stream (40), and wherein at least a portion the first for example charging of process vapour stream (40) is back to hydrogenation methanator (200).

In one embodiment, as described in Figure 1, the second heat exchanger unit (400) before having be superheat section (400a) steam boiler part (400b) both.The stream (39a) of boiler feed water can pass through steam boiler part (400b), to produce the first process vapour stream (40), pass through subsequently vapor superheater (400a), to produce the overheated process vapour stream (25a) with suitable temperature and pressure, for introduction into hydrogenation methanator (200), for example,, by mixing with feed gas stream (20).Vapor superheater (400a) also can be used for overheated other recycled vapour stream (for example the 3rd process vapour stream (43)) to being fed to the required degree of hydrogenation methanator (200) as vapour stream (25).

The raw produce stream (70) of the cooling methane rich obtaining is conventionally in following temperature, under pressure and speed, leave the second heat exchanger unit (400): temperature range is approximately 450 ℉ (approximately 232 ℃)-Yue 1100 ℉ (approximately 593 ℃), be more typically about 550 ℉ (approximately 288 ℃)-Yue 950 ℉ (approximately 510 ℃), pressure is about 50psig (about 446kPa)-Yue 800psig (about 5617kPa), be more typically about 400psig (about 2860kPa)-Yue 600psig (about 4238kPa), and speed is approximately 0.5 feet per second clock (about 0.15m/ second)-Yue 2.0 feet per second clocks (about 0.61m/ second), be more typically about 1.0 feet per second clocks (0.30m/ second)-Yue 1.5 feet per second clock (about 0.46m/ second).

Purification for gas

Purifying products can comprise, for example, sour conversion process (700) and acid gas remove (800) and optional contaminant trace species is removed (500) and optional ammonia removal and recovery (600).

Contaminant trace species is removed (500)

As those skilled in the art are familiar with, the pollution level of gas stream (for example, the raw produce of cooling methane rich stream (70)) depends on the character for the preparation of the carbonaceous material of carbon raw material.For example, some coal (such as Illinois #6) can have high sulfur content, causes higher COS to pollute; And other coal (such as Powder River Basin coal) can contain the mercury of conspicuous level, it can volatilize in hydrogenation methanator (200).

Can be by COS from gas stream (for example, the raw produce stream (70) of cooling methane rich) in remove, by COS, be hydrolyzed (referring to US3966875, US4011066, US4100256, US4482529 and US4524050), the CuSO by gas stream through particulate Wingdale (referring to US4173465), acidic buffer ₄solution (referring to US4298584), alkanolamine absorption agent, such as methyldiethanolamine, trolamine, dipropanolamine or diisopropanolamine (DIPA), contain butylidene sulfone (tetramethylene sulfone, referring to US3989811); Or there is freezing liquid CO ₂the countercurrent washing (referring to US4270937 and US4609388) of the second cooling gas stream.

HCN for example, can be removed from gas stream (, the raw produce stream (70) of cooling methane rich), by reacting to produce CO with ammonium sulfide or ammonium polysulfide ₂, H ₂s and NH ₃(referring to US4497784, US4505881 and US4508693), or use formaldehyde then by ammonium polysulfide or sodium polysulphide two stage wash (referring to US4572826), by water, absorbed (referring to US4189307), and/or the hydrolyst that passes through process alumina load is such as MoO ₃, TiO ₂and/or ZrO ₂and decompose (referring to US4810475, US5660807 and US 5968465).

Can be by element mercury from gas stream (for example, the raw produce stream (70) of cooling methane rich) in remove, for example, by absorbing (referring to US3876393) with the carbon of sulfuric acid activation, by absorbing (referring to US4491609) with the carbon of sulphur dipping, by containing H ₂the amine solvent of S absorbs (referring to US4044098), by the zeolite that floods silver or gold, absorbs (referring to US4892567), with hydrogen peroxide and methanol oxidation be HgO (referring to US5670122), at SO ₂exist lower use brominated or containing the compound oxidation (referring to US6878358) of iodine, with the plasma oxidation (referring to US6969494) containing H, Cl and O, and/or for example, by chloride oxidizing gas oxidation (, ClO, referring to US7118720).

When utilizing aqueous solution to remove any or all COS, HCN and/or during Hg, the waste water producing in contaminant trace species removal unit can be guided treatment unit for waste water (not describing) into.

When existing, the contaminant trace species of concrete contaminant trace species is removed should be from the gas stream of such processing (for example, the raw produce stream (70) of cooling methane rich) remove at least this contaminant trace species of substantial part (or essence is whole), conventionally reach in or lower than the level of the specification limit of the product flow of expecting.Conventionally, contaminant trace species is removed should remove at least 90% from the first cooling gas stream, or at least 95%, or at least 98% COS, HCN and/or mercury, based on the weight of pollutent before processing.

(600) are removed and reclaimed to ammonia

As those skilled in the art are familiar with, the gasification of biomass, some coal, some petroleum coke and/or utilize air can produce in product flow the ammonia of significant quantity for hydrogenation methanator as source of oxygen.Optionally, (for example, the raw produce stream (70) of cooling methane rich, can wash with water, to remove and to reclaim ammonia gas stream as described in Figure 3) in one or more ammonia removals and recovery unit (600).

Ammonia recycling can be for example to directly from interchanger (400) or carrying out with raw produce stream next or cooling methane rich after treatment in both (70): (i) one or more contaminant trace species removal units (500), and (ii) one or more sour conversion units (700).

After washing, gas stream (for example, the raw produce stream (70) of cooling methane rich), comprises at least H conventionally ₂s, CO ₂, CO, H ₂and CH ₄.When the raw produce stream (70) of cooling methane rich is above when peracid conversion unit (700),, after washing, gas stream comprises at least H conventionally ₂s, CO ₂, H ₂and CH ₄.

According to method known to those skilled in the art, can reclaim ammonia by washer water, ammonia can for example, reclaim usually used as aqueous solution (61) (, 20 % by weight).Scrubber waste can be transferred to treatment unit for waste water (not describing).

When existing, ammonia is removed process should for example, remove at least ammonia of substantial part (whole with essence) from the stream through washing (, the raw produce of cooling methane rich stream (70)).In the context of removing at ammonia, " essence " is removed and is referred to enough components of high per-cent of removal, makes to produce the finished product of expectation.Conventionally, ammonia removal method by remove through the first gas stream of washing at least about 95%, or at least about 97% ammonia content, the ammonia weight based in stream before treatment.

Acid transforms (700)

The raw produce of a part of or all methane rich (is for example flowed, the raw produce stream (70) of cooling methane rich) be fed to sour conversion reactor (700), with the sour conversion reaction of experience (also referred to as water gas shift reaction) under existing at aqueous medium (such as steam), with will be at least the CO of major portion (or substantial part, or essence is whole) be converted into CO ₂, and improve H ₂mark, to produce the raw produce stream (72) of hydrogen rich gas.Produce the hydrogen content improving for Optimization of Hydrogen product gas, this hydrogen product gas can separate from methane, as discussed below.

Water-gas conversion processing can be carried out the raw produce stream (70) of the cooling methane rich of directly passing through from interchanger (400), or the raw produce stream (70) of the cooling methane rich of passing through contaminant trace species removal unit (500) and/or ammonia removal unit (600) is carried out.

Acid conversion process is described in detail in for example US7074373.This process relates to and adds water, or uses the water being included in gas, and on steam reforming catalyst, makes obtained water-gas mixture adiabatic reaction.Typical steam reforming catalyst is included in one or more VIII family metals in heat-resistant carriers.

For the method and the reactor that carry out acid gas conversion reaction containing the gas stream of CO are known to the skilled person.Suitable reaction conditions and suitable reactor can become according to the amount of the CO that must exhaust from gas stream.In some embodiments, acid gas transforms and can in the single stage, carry out, and temperature range is from approximately 100 ℃, or approximately 150 ℃, or approximately 200 ℃, to approximately 250 ℃, or to approximately 300 ℃, or to approximately 350 ℃.In these embodiments, conversion reaction can carry out catalysis by any suitable catalyzer well known by persons skilled in the art.These catalyzer include, but not limited to based on Fe ₂o ₃catalyzer, such as Fe ₂o ₃-Cr ₂o ₃catalyzer, and other is based on transition metal and the catalyzer based on transition metal oxide.In other embodiments, acid gas transforms and can in multiple stages, carry out.In a specific embodiment, acid gas transforms carries out in two stages.This two phase process is used high temperature order, is then low temperature order.Air temperature ranges for pyrolytic conversion reaction is approximately 350 ℃-Yue 1050 ℃.Typical high temperature catalyst includes, but not limited to the ferric oxide of the chromic oxide combination of optional and small amount.Air temperature ranges for low temperature conversion is approximately 150 ℃-Yue 300 ℃, or approximately 200 ℃-Yue 250 ℃.Low temperature conversion catalyst includes, but not limited to load on the cupric oxide on zinc oxide or aluminum oxide.Suitable method for sour conversion process is described in the US2009/0246120A1 being incorporated to above.

Acid conversion reaction is heat release, and therefore its logical heat exchangers carries out, and such as the 4th heat exchanger unit (401), to allow, effectively utilizes heat energy.Adopt the conversion reactor of these features to be known to the skilled person.An example of suitable conversion reactor is described in the US7074373 being incorporated to above, but other design well known by persons skilled in the art is also effective.

After acid gas Transformation Program, the raw produce stream (72) of the hydrogen rich gas obtaining contains CH conventionally ₄, CO ₂, H ₂, H ₂s, steam, optional CO and optional other pollutent in a small amount.

As mentioned above, the raw produce stream (72) of hydrogen rich gas can be provided to heat recovery unit, for example, the 4th heat exchanger unit (401).Although the 4th heat exchanger unit (401) is described as independent unit in Fig. 3, it can exist like this and/or be integrated in sour conversion reactor (700), therefore can cooling sour conversion reactor (700) and remove at least a portion heat energy from the raw produce stream (72) of hydrogen rich gas, to reduce the raw produce of hydrogen rich gas, flow the temperature of (72), to produce the raw produce stream of cooling hydrogen rich gas.

The heat energy that at least a portion reclaims can be used for producing the 4th process vapour stream by water/vapour source.

In an embodiment for the election, as described in Figure 3, leaving sour conversion reactor (700) afterwards, the raw produce stream (72) of hydrogen rich gas is incorporated into superheater (401a), is then boiler feed water preheater (401b).Superheater (401a) can for example flow the stream (42a) of the part of (70) for the overheated raw produce that can be cooling methane rich, to produce overheated stream (42b), reconsolidate subsequently the raw produce stream (70) into cooling methane rich.Or the product flow of all cooling methane rich can preheating in superheater (401a), is fed to sour conversion reactor (700) subsequently as overheated stream (42b).Boiler feed water preheater (401b) can be for example for preboiler feed water (46) and produce the boiler feed water stream (39) of preheating, be used for the one or more of First Heat Exchanger unit (400), the second heat exchanger unit (140) and the 3rd heat exchanger unit (403), and other steam generation operation.

If expect some carbon monoxide contents of the raw produce stream (50) that retains methane rich, the gas bypassing loop being communicated with the first heat recovery unit (400) (71) can be provided, for example, (to allow all other peracid conversion reactors of raw produce stream (70) (700) of some cooling methane rich of leaving the first heat recovery unit (400) and the second heat recovery unit, the 4th heat exchanger unit (401)), and merge with the raw produce stream (72) of hydrogen rich gas at acid gas removal unit (800) certain point before.When expecting to reclaim independent methane byproduct, this is particularly useful, because the carbon monoxide retaining can be subsequently by methanation, as discussed below.

Acid gas is removed (800)

Acid gas removal unit (800) is subsequently removed the H of substantial part for the treated product flow (72) from hydrogen rich gas ₂the CO of S and substantial part ₂and produce processed gas stream (80).

Acid gas removal process is usually directed to make gas stream to contact with solvent, and described solvent ratio is as the solution of monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, diglycolamine, amino acid whose sodium salt, methyl alcohol, hot salt of wormwood etc., to produce load C O ₂and/or H ₂the absorption agent of S.One method can relate to uses the Selexol with two series (train)

(UOP LLC, Des Plaines, IL USA) or Rectisol

(Lurgi AG, Frankfurt am Main, Germany) solvent; Each series contains H ₂s absorption agent and CO ₂absorption agent.

For a kind of method of removing acid gas, be described in the US2009/0220406A1 being incorporated to above.

At least CO of substantial part (for example, essence is whole) ₂and/or H ₂s (with other remaining contaminant trace species) should remove by acid gas removal process.In the context of removing in acid gas, " essence " is removed and is referred to enough components of high per-cent of removal, makes to produce the finished product of expectation.Therefore, actual removal amount can be different between component and component.For " pipeline-quality Sweet natural gas ", can there is the only H of trace (at the most) ₂s, but the CO of tolerable higher amount ₂.

Conventionally, at least about 85%, or at least about 90%, or at least about 92% CO ₂, with at least about 95%, or at least about 98%, or at least about 99.5% H ₂s should remove from the raw produce stream (70) of cooling methane rich.

The loss of removing the product (hydrogen and methane) of expecting in step in acid gas should minimize, and makes processed gas stream (80) comprise at least methane and the hydrogen of the stream of the raw produce from hydrogen rich gas (72) of substantial part (whole with essence).Conventionally, this loss should be respectively from the raw produce stream methane of (72) of hydrogen rich gas and the approximately 2mol% of hydrogen or still less, or about 1.5mol% or still less, or about 1mol% or still less.

The processed gas stream (80) obtaining comprises CH conventionally ₄, H ₂with optional CO (for downstream methanation), and common a small amount of CO ₂and H ₂o.

From acid gas, remove the H of any recovery of (with other process, such as sour water stripping (SWS)) ₂s (78) can be converted into elementary sulfur by any method known to those skilled in the art, comprises Kraus process.Sulphur can be used as the liquid of melting and reclaims.

The CO of any recovery of removing from acid gas ₂(79) can be compressed, at CO ₂conveying in pipeline, industrial application and/or isolation are for storing or other process, such as the recovery of oil strengthening.

In acid gas removal unit (800) before, by knockout drum (knock-out drum) or similar water separation device (450), can process the raw produce stream (72) of hydrogen rich gas to reduce water-content.The sour wastewater streams (47) obtaining can be delivered to treatment unit for waste water (not describing), for further processing.

Hydrogen Separation (850)

According to method known to those skilled in the art, hydrogen can be separated from desulfurization product gas stream (80), for example, such as low-temperature distillation, use molecular sieve, gas delivery (, pottery) film and/or pressure-swing absorption (PSA) technology.Referring to the US2009/0259080A1 being for example incorporated to above.

In one embodiment, PSA device is for Hydrogen Separation.It is known for hydrogen is generally to person of ordinary skill in the relevant from the Fen Li PSA technology of gaseous mixture that contains methane (with optional carbon monoxide), for example, disclosed in US6379645 (quoting with other of reference wherein).PSA device is commercially available obtaining conventionally, for example, and based on deriving from Air Products and Chemicals Inc. (Allentown, PA), UOP LLC (Des Plaines, IL) and other technology.

In another embodiment, can use hydrogen membrane separator, be then PSA device.

This separation provides the processed gas stream (82) of high-purity hydrogen product flow (85) and hydrogen-depleted gas.

The purity of the hydrogen product stream (85) preferably reclaiming is at least about 99 % by mole, or at least 99.5 % by mole, or at least about 99.9 % by mole.

Hydrogen product stream (85) can be for example as the energy and/or as reactant.For example, hydrogen can be used as the energy of the fuel cell based on hydrogen, for generating and/or steam generation (referring to Fig. 3 980,982 and 984), and/or for hydrogenation methanation method subsequently.Hydrogen also can be used as reactant in different hydrogenation process, such as the hydrogenation process of finding in chemistry and petroleum refining industry.

The processed gas stream (82) of hydrogen-depleted gas comprises in fact methane, contains optional carbon monoxide (depending primarily on the degree of sour conversion reaction and bypass) in a small amount, carbonic acid gas (depending primarily on the validity of acid gas removal process) and hydrogen (depending primarily on degree and the validity of Separation Technique of Hydrogen Gas).

The processed gas stream (82) of hydrogen-depleted gas

The processed gas stream (82) of hydrogen-depleted gas comprises in fact methane, contains optional hydrogen and carbon monoxide in a small amount, and at least partly as the stream of recycled gases (30) to POx reactor (100) charging.The processed gas stream (82) of hydrogen-depleted gas also can further processing as described below and/or utilization.

In one embodiment, for hydrogen gas production is maximized, the processed gas (82) of the hydrogen-depleted gas of substantial part (or essence is whole) is used as to stream of recycled gases (30).Smaller portions (being conventionally less than approximately 10 % by weight) can be used for generating, or for combustion of feed gas body, flow the superheater of (20), as discussed above.

If expect production methane byproduct stream (99), the processed gas stream (82) of hydrogen-depleted gas is divided into stream of recycled gases (30) as major portion, and methane rich product gas stream (95) is as smaller portions.Conventionally, stream of recycled gases (30) form hydrogen-depleted gas processed gas stream (82) at least about 60 % by weight.

According to working pressure and temperature condition, stream of recycled gases (30) need to be compressed before being fed to POX reactor (100) conventionally.

Methanation (950)

Can be by all or a part of methane rich product gas stream (95) directly as methane product stream (99), maybe can by all or a part of methane rich product gas stream (95) further processings/purifying with production methane product, flow (99).

In one embodiment, methane rich product gas stream (95) is fed to and arranges methanator (950), to produce other methane by carbon monoxide and the hydrogen that can be present in methane rich product gas stream (95), cause the product flow (97) of methane rich.

Methanation reaction can carry out in any suitable reactor, for example, and single-stage methanator, a series of single-stage methanator or staged reactor.Methanator includes, but not limited to fixed bed, moving-bed or fluidized-bed reactor.Referring to for example US3958957, US4252771, US3996014 and US4235044.Methanator and catalyzer be commercially available obtaining conventionally.It is known that the catalyzer using in methanation and methanation condition are generally person of ordinary skill in the relevant, and for example depend on temperature, pressure, flow velocity and the composition of the gas stream entering.

Because methanation reaction is heat release, in different embodiments, can for example the product gas stream of methane rich (97) be further provided to heat recovery unit, for example, the 3rd heat exchanger unit (403).Although interchanger (403) is described as independent unit, it can exist like this and/or be integrated in methanator (950), therefore can cooling methanator unit and remove at least a portion heat energy from the gas stream of methane rich, to reduce the temperature of gas stream of methane rich.The heat energy reclaiming can be used for producing the 3rd process vapour stream (43) by water and/or vapour source (39c).

The product gas stream of methane rich (97) can be flowed to (99) as methane product, or can when needed it further be processed, to separate and to reclaim CH by any suitable gas separating method well known by persons skilled in the art ₄, described method includes but not limited to low-temperature distillation and uses molecular sieve or gas delivery (for example pottery) film.Other gas purification method comprises, for example, produces methane hydrate, as the US2009/0260287A being incorporated to above, US2009/0259080A1 and US2009/0246120A1 disclosed.

pipeline-quality Sweet natural gas

The invention provides method and system, in certain embodiments, described method and system can produce " pipeline-quality Sweet natural gas " by the hydrogenation methanation of carbonaceous material." pipeline-quality Sweet natural gas " typically refers to following Sweet natural gas: (1) (under standard atmosphere conditions, its calorific value is 1010btu/ft at pure methane calorific value ³) ± 5% in, (2) not moisture in fact (conventionally dew point for approximately-40 ℃ or still less), and (3) in fact contain toxicity or corrosive contaminants.In some embodiments of the present invention, the methane product stream (99) of describing in aforesaid method meets these requirements.

wastewater treatment

By the remaining pollutent in any one or more waste water that cause in contaminant trace species removal, acid conversion, ammonia removal, acid gas removal and/or catalyst recovery process, can in treatment unit for waste water, be removed, to allow the water of recirculation recovery in factory (plant) and/or to dispose the water from plant processes according to any method well known by persons skilled in the art.According to raw material and reaction conditions, these remaining pollutents can comprise, for example, and phenol, CO, CO ₂, H ₂s, COS, HCN, ammonia and mercury.For example, H ₂s and HCN can remove as follows: it is approximately 3 that waste water is acidified to pH, uses inert gas treatment acid waste water in stripping tower, and improve pH to approximately 10, and process for the second time waste water with rare gas element, with except deammoniation (referring to US5236557).H ₂s can remove as follows: under remaining coke granule exists, use oxidizer treatment waste water, with by H ₂s is converted into insoluble sulfur hydrochlorate, can or filter this insoluble sulfur hydrochlorate is removed to (referring to US4478425) by flotation.Phenol can be removed as follows: make waste water and carbonaceous char (for example, solid carbon product or the poor charcoal after catalyst recovery, the see above face) contact that contains monovalence and divalence alkaline inorganic compound, and regulate pH (referring to US4113615).Phenol also can be removed as follows: with organic solvent extraction, then in stripping tower, process waste water (referring to US3972693, US4025423 and US4162902).

process steam

The different process vapour stream (for example, 40,43 and 65) that can provide steam feed loop to be produced by energy recovery for charging.

Production process vapour stream as follows: use one or more heat recovery unit, such as interchanger (140), (400) and (403), water/vapour source (such as (39a), (39b) and (39c)) is contacted from the heat energy that the process operation by different reclaims.As mentioned above.

Can use any suitable heat recovery unit known in the art.For example, can produce with the heat energy that can utilize recovery steam boiler or any other suitable vapour generator (such as shell/tubular heat exchanger) of steam.Interchanger also can be used as the superheater of vapour stream, such as (400a) in Fig. 2, make the heat recuperation in the one or more stages by process can be used for superheated vapour to the temperature and pressure of expecting, therefore eliminate the demand of the superheater to independent burning.

Although any water source can be used for producing steam, in known boiler systems, the purified and deionization (about 0.3-1.0 μ S/cm) of conventional water, slows down corrodibility process.

In the context of the inventive method, hydrogenation methanation reaction has steam demand (temperature, pressure and volume), and the amount of process steam and process heat recuperation can be enough to provide this total steam demand at least about 85 % by weight, or at least about 90 % by weight, or at least about 94 % by weight, or at least about 97 % by weight, or at least about 98 % by weight, or at least about 99 % by weight.Remaining approximately 15 % by weight or still less, or approximately 10 % by weight or still less, or approximately 6 % by weight or still less, or approximately 3 % by weight or still less, or approximately 2 % by weight or still less, or approximately 1 % by weight or still less, can be by supplementing vapour stream supply, it can be used as vapour stream (25) (or as vapour stream (25) a part) and is fed to system.

Suitable steam boiler or vapour generator can be used for providing supplementary vapour stream.This boiler can provide power as follows, for example, by using any carbonaceous material such as Powdered coal, biomass etc., and includes but not limited to the carbonaceous material (for example, fines, sees above face) of being refused by raw material preparation manipulation.

In another embodiment, for all in fact total steam demand that are applied to hydrogenation methanation reaction, wherein there is not in fact supplementary vapour stream in process vapour stream.

In another embodiment, produce excessive process steam.Excessive steam can be for example for generating electricity by steam turbine, and/or in fluidized bed dryer dried carbon raw material to the moisture content of the reduction of expecting, as discussed below.

generating

A part of methane product can be flowed to (99) for burning (980) and steam generation (982), and the hydrogen of a part of any recovery (85) is passable.As mentioned above, excessive recycled vapour can be provided to one or more generators (984), such as gas turbine or steam turbine, to generate electricity, described electricity can utilize or can be in electric online spending in factory.

the preparation of carbon raw material

Carbonaceous material processing (190)

Carbonaceous material (such as biomass and abiotic matter) can be according to any method known in the art (crushing and wet or dry grinding such as impacting), by crushing and/or grinding, prepare separately or jointly, to obtain one or more carbonaceous particulates.According to the method for crushing and/or grind carbonaceous material source, (the carbonaceous particulate obtaining can be distinguished by size, according to apart), to be provided for the carbon raw material (32) of catalyst cupport process (350), to be formed for the carbon raw material (31+32) of catalysis of hydrogenation methanator (200).

Any method well known by persons skilled in the art can be used for particulate to distinguish by size.For example, distinguish by size and can through a sieve or multiple sieve, carry out by screening or by particulate.Screening plant can comprise grizzly, diagrid and wire-mesh screen.Sieve can be static or shakes or vibratory screening apparatus in conjunction with mechanism.Or, can carry out separating carbonaceous particulate with classification.Sorting equipment can comprise preparator, gas cyclone, hydrocyclone, rake classifier, rotation whirl screen or fluidized classification device.Also carbonaceous material can be distinguished by size or classification before grinding and/or crushing.

It is from approximately 25 microns that carbonaceous particulate can be used as median size, or from approximately 45 microns to the highest approximately 2500 microns, or the fine particles supply of the highest approximately 500 microns.Those skilled in the art can easily be identified for the suitable particle diameter of carbonaceous particulate.For example, when using during fluidized-bed reactor, this carbonaceous particulate can have can gas velocity used in fluidized-bed reactor under the median size of initial stage fluidisation carbonaceous material.For the particle size range of the expectation of hydrogenation methanator (200) within the scope of Geldart A and Geldart B (comprise between the two overlapping), this depends on fluidization conditions, conventionally has limited amount thin (lower than approximately 25 microns) and thick (being greater than approximately 250 microns) material.

In addition, some carbonaceous material (for example, maize straw and switchgrass) and industrial waste (such as sawdust) may be according to crushing or grinding operation processing, or may be not suitable for former state and use, for example, due to ultra-fine grain diameter.Can make these materials be formed as having pellet or the agglomerate of suitable dimension, for crushing or be directly used in for example fluidized-bed reactor.Conventionally, pellet can be by compressing one or more carbonaceous materials to prepare; For example, referring to the US2009/0218424A1 being incorporated to above.In other example, can make biological material and coal be formed as agglomerate, described at US4249471, US4152119 and US4225457.In the following discussion, these pellets or agglomerate can exchange and use with carbonaceous particulate above.

According to the quality in carbonaceous material source, may essential other raw material treatment step.Biomass can contain high moisture content, such as green plants and grass, and can need to be dried before crushing.Municipal waste and dirt also can contain high moisture content, can for example by working pressure machine or roller mill, reduce (for example, US4436028).Equally, abiotic matter (such as hydrogenous coal) can need to be dried before crushing.Some coking coals can need partial oxidation to simplify the operation.Can carry out pre-treatment to produce other ion exchange sites, to promote catalyst cupport and/or association to the abiotic raw material (such as hard coal or petroleum coke) that lacks ion exchange sites.These pre-treatment can complete (for example, referring to the US4468231 being incorporated to and GB1599932) above by the known in the art any method that produces the position of energy ion-exchange and/or the porosity of enhancing raw material.Oxidisability pre-treatment can complete with any oxygenant known in the art.

Can consider based on the technology of abiotic matter and biomass sources, process economy, operability and approximation and be chosen in ratio and the type of carbonaceous material in carbonaceous particulate.The operability and the approximation that are used for the source of carbonaceous material can affect the price of charging, and therefore affect the total cost of production of catalysis gasification method.For example, according to treatment condition, biomass and abiotic material can be by following blend: approximately 5: 95, and approximately 10: 90, approximately 15: 85, approximately 20: 80, approximately 25: 75, approximately 30: 70, approximately 35: 65, approximately 40: 60, approximately 45: 55, approximately 50: 50, approximately 55: 45, approximately 60: 40, approximately 65: 35, approximately 70: 20, approximately 75: 25, approximately 80: 20, approximately 85: 15, approximately 90: 10, or approximately 95: 5, by wet basis or butt weighing scale.

Significantly, carbonaceous material source, and the ratio of the single component of carbonaceous particulate (for example, biomass particulate and abiotic matter particulate) can be used for controlling other material behavior of carbonaceous particulate.(what abiotic material (such as coal) and some biological material (such as rice husk) generally included significant quantity forms inorganic oxide in catalytic gasification device, ash content) inorganic substance, comprise calcium, aluminum oxide and silicon-dioxide.At the temperature that exceedes approximately 500 ℃-Yue 600 ℃, potassium and other basic metal can with ash content in aluminum oxide and silicon dioxde reaction, to form insoluble alkaline silico-aluminate.Under this form, basic metal is water insoluble in fact and as catalyzer non-activity.In order to prevent the residue build-up in hydrogenation methanator (200), the solid that can take out routinely the by product charcoal (52) that comprises ash content, unreacted carbonaceous material and different other compound (such as alkali metal compound, water-soluble and water-insoluble) purifies.

In preparation carbonaceous particulate, the ash oontent of different carbonaceous materials may be selected to be for example approximately 20 % by weight or still less, or approximately 15 % by weight or still less, or approximately 10 % by weight or still less, or approximately 5 % by weight or still less, this depends on the initial ash content in ratio and/or the different carbonaceous material of for example different carbonaceous materials.In other embodiments, the carbonaceous particulate obtaining can comprise from approximately 5 % by weight, or from approximately 10 % by weight, to approximately 20 % by weight, or to the ash oontent of approximately 15 % by weight scopes, based on the weight of carbonaceous particulate.In other embodiments, the ash oontent of carbonaceous particulate can comprise and be less than approximately 20 % by weight, or is less than approximately 15 % by weight, or is less than approximately 10 % by weight, or is less than approximately 8 % by weight, or is less than approximately 6 % by weight aluminum oxide, based on the weight of ash content.In certain embodiments, carbonaceous particulate can comprise the ash oontent that is less than approximately 20 % by weight, and based on the weight of raw material of processing, and the ash oontent of carbonaceous particulate comprises and is less than approximately 20 % by weight aluminum oxide, or be less than approximately 15 % by weight aluminum oxide, based on the weight of ash content.

In carbonaceous particulate, this lower aluminum oxide value makes the finally loss of catalyzer (particularly base metal catalysts) reduction in the hydrogenation methanation part of method.As mentioned above, aluminum oxide can react with alkaline source, to obtain comprising the insoluble charcoal of for example basic aluminate or silico-aluminate.This insoluble charcoal can cause reducing catalyst recovery (that is, improve catalyst loss), therefore, need to be in overall process the other cost of make-up catalyst.

In addition, the carbonaceous particulate obtaining can have significantly higher % carbon, therefore has significantly higher btu/lb value and the carbonaceous particulate of methane product/unit weight.In certain embodiments, the carbon content scope of the carbonaceous particulate obtaining can be from approximately 75 % by weight, or from approximately 80 % by weight, or from approximately 85 % by weight, or from approximately 90 % by weight, to the highest approximately 95 % by weight, based on the combination weight of abiotic matter and biomass.

In an example, for example, by abiotic matter and/or biomass wet lapping and differentiation by size (, to the size distribution of about 25-approximately 2500 μ m), and drain subsequently its free water (that is, dehydration) to wet cake denseness.For wet lapping, by size distinguish and the example of the suitable method of dewatering for those skilled in the art known; For example,, referring to the US2009/0048476A1 being incorporated to above.According to an embodiment of the present disclosure, the moisture content scope of the abiotic matter forming by wet lapping and/or the filter cake of biomass particulate can be about 40%-approximately 60%, or about 40%-approximately 55%, or lower than 50%.It will be appreciated by the skilled addressee that the moisture content of the carbonaceous material of the wet lapping of dehydration depends on particular type, size distribution and the concrete dehydration equipment used of carbonaceous material.Can, by this filter cake thermal treatment, as described herein, to produce one or more, low-moisture carbonaceous particulate fall.

One or more carbonaceous particulates can have unique composition separately, as mentioned above.For example, can utilize two kinds of carbonaceous particulates, wherein the first carbonaceous particulate comprises one or more biological materials, and the second carbonaceous particulate comprises one or more abiotic materials.Or, utilize the single carbonaceous particulate that comprises one or more carbonaceous materials.

For the catalyst cupport (350) of hydrogenation methanation

Hydrogenation methanation catalyst at least above-mentioned reaction of catalysis (I), (II) and (III) has activity potentially.This catalyzer is that person of ordinary skill in the relevant is known under common implication, and can comprise, for example, and basic metal, alkaline-earth metal and transition metal and their compound and complex compound.Conventionally, hydrogenation methanation catalyst is basic metal, such as disclosed in many reference that are incorporated to above.

For hydrogenation methanation reaction, conventionally one or more carbonaceous particulates are further processed, with at least one hydrogenation methanation catalyst that associates, it comprises at least one alkali-metal source conventionally, to produce the carbon raw material (31+32) of catalysis.

The carbonaceous particulate that is provided for catalyst cupport can be through processing the carbon raw material (31+32) to form catalysis, led to hydrogenation methanator (200), or be divided into one or more processing stream, wherein at least one processes stream and the association of hydrogenation methanation catalyst, to form at least one feedstream through catalyst treatment.Remaining is processed stream and can, for example through processing, make it to associate with second component.In addition, can process for the second time the feedstream through catalyst treatment, make it to associate with second component.This second component can be for example the second hydrogenation methanation catalyst, promotor or other additive.

In an example, main hydrogenation methanation catalyst (for example can be provided to single carbonaceous particulate, potassium and/or sodium source), then be independent processing, for example, (to provide one or more promotors and additive to identical single carbonaceous particulate, calcium source), to obtain the carbon raw material (31+32) of catalysis.For example,, referring to the US2009/0217590A1 being incorporated to above and US2009/0217586A1.Hydrogenation methanation catalyst and second component also can be used as mixture and to single the second carbonaceous particulate, provide in single processing, to obtain the carbon raw material (31+32) of catalysis.

When one or more carbonaceous particulates are provided for catalyst cupport, at least one carbonaceous particulate and hydrogenation methanation catalyst associate, to form at least one feedstream through catalyst treatment.In addition, any carbonaceous particulate can be divided into as detailed above to one or more processing stream, for make it with second or other component associate.The stream obtaining can any combination blend, and so that the carbon raw material (31+32) of catalysis to be provided, condition is at least one feedstream that is used to form catalysis through the feedstream of catalyst treatment.

In one embodiment, at least one carbonaceous particulate and hydrogenation methanation catalyst and optional second component associate.In another embodiment, each carbonaceous particulate and hydrogenation methanation catalyst and optional second component associate.

Any method well known by persons skilled in the art can be used for one or more hydrogenation methanation catalysts and any carbonaceous particulate and/or processes stream associating.These methods include but not limited to, mix and impregnated catalyst on treated carbonaceous material with solid catalyst source.Some dipping methods well known by persons skilled in the art can be used for being incorporated to hydrogenation methanation catalyst.These methods include but not limited to, the wet combination of dipping, vapo(u)rability dipping, vacuum impregnation, immersion dipping, ion-exchange and these methods of initial stage.

In one embodiment, by load groove with solution (for example, the water-based) pulp of catalyzer, metal hydride alkaline methanation catalyst can be immersed in to one or more carbonaceous particulates and/or process in stream.When with the solution pulp of catalyzer and/or promotor, can, by obtained de-watering of slurries, so that the feedstream through catalyst treatment to be provided, be generally equally wet cake.In the methods of the invention, catalyst solution can be prepared by any catalyst source, comprises fresh or make-up catalyst and catalyst recycle or catalyst solution.For making de-watering of slurries comprise filtration (gravity or vacuum), centrifugal and hydraulic pressure to provide through the method for the wet cake of the feedstream of catalyst treatment.

In another embodiment, as the U.S. Patent Application Serial Number 12/648 being incorporated to above, disclosed in 469, by carbonaceous particulate and the combination of aqueous catalyst solution, to produce the wet cake of not draining in fact, under the temperature condition raising, mix subsequently, final drying is to suitable moisture level.

Be applicable to coal particulate and/or the processing stream that comprises coal and hydrogenation methanation catalyst to combine to provide through a kind of concrete method of the feedstream of catalyst treatment for by ion-exchange, as described in the US2009/0048476A1 being incorporated to above and U.S. Patent Application Serial Number 12/648,471.Based on the adsorption isothermal line to the specific formation of coal, by the catalyst cupport maximizing of ion-exchange mechanism, as what discussed in the reference being incorporated to.This load provides feedstream through catalyst treatment as wet cake.Can be controlled in the other catalyzer that (being included in inside, hole) retains on the wet cake of particulate of ion-exchange, make to obtain in a controlled manner total catalyst target value.By controlling the concentration of catalyst component in solution, and duration of contact, temperature and method, the total amount of the catalyzer of controllable load, as disclosed in the aforementioned reference being incorporated to, and based on the characteristic of initial coal, person of ordinary skill in the relevant can easily determine in addition.

In another example, carbonaceous particulate and/or process the processing of the available hydrogenation methanation catalyst of stream, and second process the available second component processing of stream (referring to the US2007/0000177A1 being incorporated to) above.

By carbonaceous particulate, process stream and/or can any combination blend by the aforementioned feedstream through catalyst treatment obtaining, so that the second carbon raw material of catalysis to be provided, condition is at least one carbon raw material (31+32) that is used to form catalysis through the feedstream of catalyst treatment.Finally, the carbon raw material of catalysis (31+32) is led on hydrogenation methanator (200).

Conventionally, each catalyst-supported units comprises at least one load groove, makes one or more carbonaceous particulates and/or process stream to contact with the solution that comprises at least one hydrogenation methanation catalyst, to form one or more feedstreams through catalyst treatment.Or catalyst component can be used as solia particle and is blended into one or more carbonaceous particulates and/or processes in stream, to form one or more feedstreams through catalyst treatment.

Conventionally, when hydrogenation methanation catalyst is basic metal, it is present in proportional range that amount in the carbon raw material of catalysis is enough to provide alkali metal atom and carbon atom in microparticle compositions for from approximately 0.01, or from approximately 0.02, or from approximately 0.03, or from approximately 0.04, to approximately 0.10, or to approximately 0.08, or to approximately 0.07, or to approximately 0.06.

Together with some raw materials, alkaline components also can provide in the carbon raw material of catalysis, to realize approximately 10 times of the approximately 3-(based on quality) of the ash oontent of the combination of carbonaceous material in the carbon raw material of alkali metal content as many as catalysis.

Suitable basic metal is lithium, sodium, potassium, rubidium, caesium and their mixture.Useful especially is potassium source.Suitable alkali metal compound comprises alkaline carbonate, supercarbonate, formate, oxalate, amide, oxyhydroxide, acetate or similar compound.For example, catalyzer can comprise one or more in sodium carbonate, salt of wormwood, rubidium carbonate, Quilonum Retard, cesium carbonate, sodium hydroxide, potassium hydroxide, rubidium hydroxide or cesium hydroxide, particularly, and salt of wormwood and/or potassium hydroxide.

Can utilize optional promotor or other catalyst additive, such as in the reference being incorporated to above disclosed those.

Combination conventionally comprises and is greater than approximately 50% with one or more feedstreams through catalyst treatment of the carbon raw material of formation catalysis, be greater than approximately 70%, or be greater than approximately 85%, or be greater than the total amount of the catalyzer of load approximately 90% and carbon raw material catalysis (31+32) association.The per-cent of the catalyzer of the total loading of associating from the different feedstreams through catalyst treatment can be determined according to method known to those skilled in the art.

Independent carbonaceous particulate, through the feedstream of catalyst treatment with process suitably blend of stream, to control, for example, the total catalyst load of the carbon raw material of catalysis (31+32) or other are measured, as previously discussed.The suitable ratio of the various flows of combination depends on the character of the expectation of the amount of the carbonaceous material that comprises each stream and the carbon raw material of catalysis (31+32).For example, the abiotic matter particulate stream of biomass particulate stream and catalysis can combine, and its ratio obtains the carbon raw material (31+32) of the catalysis with predetermined ash oontent, as previously discussed.

Any aforementioned feedstream through catalyst treatment, processing stream and treated feedstream, as one or more dry particulates and/or one or more wet cakes, can combine by any method known to those skilled in the art, described method includes but not limited to, mediate and horizontal or vertical mixing machine, for example, single screw rod or twin screw, ribbon or drum mixer.The carbon raw material (31+32) of the catalysis obtaining can store for using or be transferred to one or more feed operation in the future, for introduction into hydrogenation methanator.According to any method well known by persons skilled in the art, the carbon raw material of catalysis can be transported to and store or feed operation, described method is screw rod transveyer or pneumatic transport for example.

In addition excessive moisture can be removed from the carbon raw material (31+32) of catalysis.For example, the available fluid bed slurry dryer of carbon raw material (31+32) of catalysis is dry (, use overheated steam treatment, with vaporised liquid), or under vacuum or under inert gas flows by solution thermal evaporation or remove, so that the carbon raw material of catalysis to be provided, its remaining moisture content is for example approximately 10 % by weight or still less, or approximately 8 % by weight or still less, or approximately 6 % by weight or still less, or approximately 5 % by weight or still less, or approximately 4 % by weight or still less.In this case, expect to utilize the steam being produced by process heat recuperation.

Catalyst recovery (300)

The carbon raw material (31+32) of catalysis reacts raw produce stream (50) and solid carbon by product (52) that methane rich is provided by hydrogenation methanator (200) conventionally under described condition.The catalyzer that solid carbon by product (52) conventionally comprises a certain amount of unreacted carbon, inorganic ash content and carries secretly.Solid carbon by product (52) can be exported from hydrogenation methanator (200) and be removed by charcoal, for sampling, purification and/or catalyst recovery.

Term used herein " catalyzer of carrying secretly " refers to the compound of the catalytic activity part that comprises hydrogenation methanation catalyst, such as alkaline components.For example, " catalyzer of carrying secretly " can include, but not limited to soluble alkali metal compound (such as basic carbonate, alkaline hydrated oxide and basic oxide) and/or insoluble basic cpd (such as alkaline silico-aluminate).Character and their recovery method of the catalyst component associating with the charcoal that extracted by catalytic gasification device discuss in detail in the US2007/0277437A1 being incorporated to above, US2009/0165383A1, US2009/0165382A1, US2009/0169449A1 and US2009/0169448A1.

Solid carbon by product (52) can be exported from hydrogenation methanator (200) and periodically be taken out by charcoal, and described charcoal outlet is lock-hopper system, but known other method of those skilled in the art.The method of removing solid carbon product is known to the skilled person.For example, can adopt a kind of such method of being instructed by EP-A-0102828.

Charcoal by product (52) from hydrogenation methanator (200) can lead to catalyst recovery unit (300), as described below.This charcoal by product (52) also can be divided into multiple stream, one of them can lead to catalyst recovery unit (300), and another stream (54) can for example be used as methanation catalyst (as described in the US2010/0121125A1 being incorporated to above) and not do catalyst recovery processing.

In certain embodiments, when hydrogenation methanation catalyst is basic metal, basic metal in recyclable solid carbon by product (52), with production catalyst recycle stream (56), and any catalyzer not reclaiming can flow by catalyst make-up (58) compensation.In raw material, aluminum oxide adds that silicon-dioxide is more, and the cost that obtains higher basic metal recovery is higher.

In one embodiment, from the available recycle gas of solid carbon by product (52) and the shrend of hydrogenation methanator (200), go out, the catalyzer of carrying secretly to extract a part.The catalyzer (56) reclaiming can be guided catalyst-supported units (350) into, for the recycling of base metal catalysts.Poor charcoal (59) can for example guide into any one or more raw material preparation manipulations (190) for recycling in the raw material, burning of preparation catalysis for one or more vapour generators provide power (such as the US2009/0165376A1 being incorporated to above and US2009/0217585A1 disclosed) or like this for multiple application, for example,, as absorption agent (such as disclosed in the US2009/0217582A1 being incorporated to above).

Other useful especially recovery and method for recycling are described in US4459138, and the US2007/0277437A1 being incorporated to above, US2009/0165383A1, US2009/0165382A1, US2009/0169449A1 and US2009/0169448A1.Further method details can be with reference to those files.

Can be by the combination of catalyst recycle to catalyst cupport process or catalyst cupport process.For example, the catalyzer of all recirculation can be fed to a catalyst cupport process, and another process is only utilized make-up catalyst.In multiple catalyst cupport processes, also can on single basis, control the catalyst recycle level relative with make-up catalyst.

Multi-series method

In the method for the invention, each method can be carried out in one or more processing units.For example, can supply the carbon raw material from one or more catalyst cupports and/or feed preparation unit operation to one or more hydrogenation methanators.Similarly, according to concrete system architecture, the raw produce stream of the methane rich being produced by one or more hydrogenation methanators can be processed or purifying in the combination of interchanger, sour conversion unit, acid gas removal unit and/or hydrogen gas segregator unit separately or by them, as what discussed in the US2009/0324458A1 being for example incorporated to above, US2009/0324459A1, US2009/0324460A1, US2009/0324461A1 and US2009/0324462A1.

In certain embodiments, described method is utilized two or more hydrogenation methanators (for example, 2-4 hydrogenation methanator).In these embodiments, (described method can contain the processing unit dispersed before hydrogenation methanator, be less than the sum of hydrogenation methanator), for the carbon raw material of catalysis is finally provided to multiple hydrogenation methanators, and/or the processing unit that contains convergence after hydrogenation methanator (, be less than the sum of hydrogenation methanator), for the treatment of the raw produce of the multiple methane rich that produced by multiple hydrogenation methanators, flow.

For example, the catalyst-supported units that described method can utilize (i) to disperse, to provide the carbon raw material of catalysis to hydrogenation methanator; (ii) the carbonaceous material processing unit of dispersing, to provide carbonaceous particulate to catalyst-supported units; (iii) interchanger of assembling, to accept the raw produce stream from multiple methane rich of hydrogenation methanator; (iv) the sour conversion reactor of assembling, to accept the raw produce stream from the multiple cooling methane rich of interchanger; (v) the acid gas removal unit of assembling, to accept the raw produce gas stream from multiple hydrogen rich gass of sour conversion reactor; Or (vi) hydrogen separation unit assembled, to accept the multiple processed gass stream from acid gas removal unit.

When processing unit that system contains convergence, can select the processing unit of each convergence to there is the ability of the 1/n part of accepting the total gas stream that is greater than the processing unit that is fed to convergence, wherein n is the quantity of the processing unit assembled.For example, in the method for utilizing 4 hydrogenation methanators and 2 interchanger (for accepting the raw produce stream from 4 methane rich of hydrogenation methanator), can select heat transfer equipment to have to accept the ability of 1/2 (for example 1/2 to 3/4) of the total gas volume that is greater than 4 gas streams, and be communicated with two or more hydrogenation methanators, to allow the General Maintenance of one or more interchanger, and without closing whole treatment system.

Similarly, when system contains the processing unit of dispersing, the processing unit that can select each to disperse has the ability of the 1/m part of the total feed stream of accepting to be greater than the processing unit that supply assembles, and wherein m is the quantity of the processing unit dispersed.For example, in the method for utilizing 2 catalyst-supported units and single carbonaceous material processing unit (for carbonaceous particulate is provided to catalyst-supported units), the catalyst-supported units that can select to be communicated with carbonaceous material processing unit separately have accept from the cumulative volume of the carbonaceous particulate of single carbonaceous material processing unit 1/2 to whole abilities, to allow the General Maintenance of one of catalyst-supported units, and without closing whole treatment system.

Claims (11)

1. by carbon raw material, produce multiple gaseous product and produce the method that hydrogen product flows, said method comprising the steps of:

(a) to hydrogenation methanator, supply

(1) carbon raw material,

(2) hydrogenation methanation catalyst,

(3) vapour stream,

(4) feed gas stream and

(5) the first optional oxygen enriched gas stream;

(b) under carbon monoxide, hydrogen, steam, hydrogenation methanation catalyst and optional oxygen exist, in hydrogenation methanator, make carbon raw material reaction, to produce the raw produce stream of the methane rich that comprises methane, carbon monoxide, hydrogen, carbonic acid gas, hydrogen sulfide and heat energy;

(c) from described hydrogenation methanator, take out the raw produce stream of described methane rich;

(d) the raw produce stream of described methane rich is introduced in First Heat Exchanger unit, with the raw produce stream from described methane rich, removed heat energy;

(e) acid transforms the carbon monoxide of at least major portion in the raw produce stream of described methane rich, to produce the raw produce stream of the hydrogen rich gas that comprises hydrogen, methane, carbonic acid gas, hydrogen sulfide and optional carbon monoxide;

(f) from the raw produce stream of described hydrogen rich gas, remove the carbonic acid gas of substantial part and the hydrogen sulfide of substantial part, with the raw produce stream from described hydrogen rich gas, produce the processed gas stream of the hydrogen that comprises substantial part, methane and optional carbon monoxide;

(g) from described processed gas flow point from the hydrogen of major portion at least, the processed gas stream of the hydrogen-depleted gas of the carbon monoxide that comprises methane, optional existence in described processed gas stream with production (1) hydrogen product stream and (2) and optional hydrogen, at least 99mol% of purity of wherein said hydrogen product stream;

(h) optionally make the processed gas stream of hydrogen-depleted gas be divided into stream of recycled gases and methane rich product gas stream;

(i) if supply stream of recycled gases and the second oxygen enriched gas stream that the processed gas of the hydrogen-depleted gas of at least a portion flows or exists to partial oxidation reactor; With

(j) if the stream of recycled gases of the processed gas stream of supplied hydrogen-depleted gas or the supply of existence is reacted in partial oxidation reactor with oxygen, to produce heat energy and feed gas stream, wherein said feed gas stream comprises carbon monoxide, hydrogen and steam

Wherein the described reaction in step (b) has synthetic gas demand, if and the processed gas that is fed to the hydrogen-depleted gas of described partial oxidation reactor flows or the amount of the stream of recycled gases of existence is at least enough to produce enough carbon monoxide and hydrogen in described feed gas stream, at least to meet the synthetic gas demand of the described reaction in step (b).

2. the method for claim 1, the mole number that the raw produce stream that it is characterized in that methane rich comprises methane, carbonic acid gas, carbon monoxide and hydrogen in the raw produce stream based on methane rich at least methane, carbonic acid gas, carbon monoxide and the hydrogen in 20mol% methane and the stream of the raw produce based on methane rich mole number at least 50mol% methane add carbonic acid gas.

3. the method for claim 1, is characterized in that hydrogenation methanation catalyst comprises basic metal.

4. the method for claim 1, is characterized in that in step (b), producing charcoal by product, and described charcoal by product is taken out continuously or periodically from hydrogenation methanator; Hydrogenation methanation catalyst comprises basic metal; Charcoal by product comprises the alkali metal content from hydrogenation methanation catalyst; At least a portion charcoal by product is processed to reclaim at least a portion alkali metal content; The alkali metal content recirculation that at least a portion is reclaimed is as hydrogenation methanation catalyst; By hydrogenation methanation catalyst dipping for carbon raw material, be fed to subsequently hydrogenation methanator, and the hydrogenation methanation catalyst that comprises recirculation for the hydrogenation methanation catalyst of impregnated carbon raw material and supplementary hydrogenation methanation catalyst.

5. the method for claim 1, is characterized in that described method is continuation method, wherein step (a-g), optional (h) and (i-j) operation in a continuous manner.

6. the method for claim 1, it is characterized in that hydrogenation methanator at least 700 °F (371 ℃) temperature and the 250psig (1825kPa to 1500 °F (816 ℃), absolute pressure) to the pressure of 800psig (5617kPa, absolute pressure), operate.

7. the method for claim 1, is characterized in that the described reaction in step (b) has steam demand; Described carbon raw material optionally comprises moisture content; Described the first oxygen enriched gas stream, if existed, optionally comprises steam; Described vapour stream, be included in the steam in described feed gas stream, described carbon raw material the optional moisture content existing and in described the first oxygen enriched gas stream the optional steam existing meet in fact described steam demand.

8. the method for claim 1, is characterized in that the described reaction in step (b) has heat demand; And the vapour stream and the feed gas stream that are fed to hydrogenation methanator comprise heat energy, described heat energy combines is enough at least meet the heat demand of the described reaction in step (b).

9. the method for claim 1, is characterized in that the heat energy of removing in First Heat Exchanger unit for generation of the first process vapour stream; By introducing the second heat exchanger unit from the feed gas stream of step (j) to remove the heat energy from feed gas stream, subsequently feed gas stream is fed to hydrogenation methanator; And by the heat energy of removing in the second heat exchanger unit for generation of the second process vapour stream.

10. the method for claim 1, the amount of the carbon monoxide that produces in partial oxidation reactor and hydrogen that it is characterized in that exceedes the synthetic gas demand of hydrogenation methanator, and step (e) before by a part of feed gas diverting flow and with the raw produce gas stream combination of methane rich.

The method of 11. claim 1-10 any one, is characterized in that not existing step (h), and to partial oxidation reactor, supplies the processed gas stream of the hydrogen-depleted gas of substantial part.

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